High-efficiency perfume capsules

ABSTRACT

The present application relates to high efficiency particles and compositions, such as consumer products, comprising such high efficiency particles as well as processes for making and using such high efficiency particles and compositions comprising such high efficiency particles. Such high efficiency particles and compositions provide enhanced benefit agent delivery to a situs that is treated with such high efficiency particles and compositions.

FIELD OF INVENTION

The present application relates to high efficiency encapsulates andcompositions, such as consumer products, comprising such high efficiencyencapsulates as well as processes for making and using such highefficiency encapsulates and compositions comprising such high efficiencyencapsulates.

BACKGROUND OF THE INVENTION

Benefit agents, such as perfumes, silicones, waxes, flavors, vitaminsand fabric softening agents, are expensive and/or generally lesseffective when employed at high levels in consumer products, forexample, personal care compositions, cleaning compositions, and fabriccare compositions. As a result, there is a desire to maximize theeffectiveness of such benefit agents. One method of achieving suchobjective is to improve the delivery efficiencies of such benefitagents. Unfortunately, it is difficult to improve the deliveryefficiencies of benefit agents as such agents may be lost do to theagents' physical or chemical characteristics, or such agents may beincompatible with other compositional components or the situs that istreated.

One method of improving the delivery efficiency of a benefit agent is toencapsulate such benefit agent. While such efforts may improve thedelivery efficiency of the benefit agent, further delivery efficiencyimprovements are desired as encapsulated benefit agents may be lostbefore or after they are applied to the situs of interest due to factorssuch as mechanical or chemical interactions, for example the action ofwash and or rinse liquors, and/or charge interactions. In certainapplications, the deposition of encapsulated benefit agents is improvedby coating the encapsulated benefit agent with a polymers. In general,such polymer coating improves the deposition of the encapsulates.However, when multiple surfaces are treated simultaneously, for example,a load of laundry containing a variety of fabrics, each surface istypically treated to a different degree (more or less benefit agentbeing delivered). For cases where the benefit agent is a perfume, thedifferent treatment levels on the different fabrics of a wash load, canlead to too strong odor on some fabrics and to too weak an odor on otherfabrics. Applicants recognized that the source of the unequal treatmentproblem was primarily due to preferential encapsulate deposition thatwas driven by the polymeric deposition aid. Thus what is needed areencapsulated benefit agents that have a high and even deposition profileacross multiple different surfaces.

In the present application, Applicants disclose encapsulated benefitagents and specific classes of amine containing polymers that, whencombined, provide a high and even deposition profile across multipledifferent surfaces, for example, hair, skin, and multiple fabrics suchas cotton, high surface cottons, polycotton and polyester.

SUMMARY OF THE INVENTION

The present application relates to high efficiency encapsulates andcompositions, such as consumer products, comprising such high efficiencyencapsulates as well as processes for making and using such highefficiency encapsulates and compositions comprising such high efficiencyencapsulates.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein “consumer product” means baby care, beauty care, fabric &home care, family care, feminine care, health care, snack and/orbeverage products or devices generally intended to be used or consumedin the form in which it is sold. Such products include but are notlimited to diapers, bibs, wipes; products for and/or methods relating totreating hair (human, dog, and/or cat), including, bleaching, coloring,dyeing, conditioning, shampooing, styling; deodorants andantiperspirants; personal cleansing; cosmetics; skin care includingapplication of creams, lotions, and other topically applied products forconsumer use including fine fragrances; and shaving products, productsfor and/or methods relating to treating fabrics, hard surfaces and anyother surfaces in the area of fabric and home care, including: air careincluding air fresheners and scent delivery systems, car care,dishwashing, fabric conditioning (including softening and/or freshing),laundry detergency, laundry and rinse additive and/or care, hard surfacecleaning and/or treatment including floor and toilet bowl cleaners, andother cleaning for consumer or institutional use; products and/ormethods relating to bath tissue, facial tissue, paper handkerchiefs,and/or paper towels; tampons, feminine napkins; products and/or methodsrelating to oral care including toothpastes, tooth gels, tooth rinses,denture adhesives, tooth whitening; over-the-counter health careincluding cough and cold remedies, pain relievers, RX pharmaceuticals,pet health and nutrition; processed food products intended primarily forconsumption between customary meals or as a meal accompaniment(non-limiting examples include potato chips, tortilla chips, popcorn,pretzels, corn chips, cereal bars, vegetable chips or crisps, snackmixes, party mixes, multigrain chips, snack crackers, cheese snacks,pork rinds, corn snacks, pellet snacks, extruded snacks and bagelchips); and coffee.

As used herein, the term “cleaning and/or treatment composition” is asubset of consumer products that includes, unless otherwise indicated,beauty care, fabric & home care products. Such products include, but arenot limited to, products for treating hair (human, dog, and/or cat),including, bleaching, coloring, dyeing, conditioning, shampooing,styling; deodorants and antiperspirants; personal cleansing; cosmetics;skin care including application of creams, lotions, and other topicallyapplied products for consumer use including fine fragrances; and shavingproducts, products for treating fabrics, hard surfaces and any othersurfaces in the area of fabric and home care, including: air careincluding air fresheners and scent delivery systems, car care,dishwashing, fabric conditioning (including softening and/or freshing),laundry detergency, laundry and rinse additive and/or care, hard surfacecleaning and/or treatment including floor and toilet bowl cleaners,granular or powder-form all-purpose or “heavy-duty” washing agents,especially cleaning detergents; liquid, gel or paste-form all-purposewashing agents, especially the so-called heavy-duty liquid types; liquidfine-fabric detergents; hand dishwashing agents or light dutydishwashing agents, especially those of the high-foaming type; machinedishwashing agents, including the various tablet, granular, liquid andrinse-aid types for household and institutional use; liquid cleaning anddisinfecting agents, including antibacterial hand-wash types, cleaningbars, mouthwashes, denture cleaners, dentifrice, car or carpet shampoos,bathroom cleaners including toilet bowl cleaners; hair shampoos andhair-rinses; shower gels, fine fragrances and foam baths and metalcleaners; as well as cleaning auxiliaries such as bleach additives and“stain-stick” or pre-treat types, substrate-laden products such as dryeradded sheets, dry and wetted wipes and pads, nonwoven substrates, andsponges; as well as sprays and mists all for consumer or/andinstitutional use; and/or methods relating to oral care includingtoothpastes, tooth gels, tooth rinses, denture adhesives, toothwhitening.

As used herein, the term “fabric and/or hard surface cleaning and/ortreatment composition” is a subset of cleaning and treatmentcompositions that includes, unless otherwise indicated, granular orpowder-form all-purpose or “heavy-duty” washing agents, especiallycleaning detergents; liquid, gel or paste-form all-purpose washingagents, especially the so-called heavy-duty liquid types; liquidfine-fabric detergents; hand dishwashing agents or light dutydishwashing agents, especially those of the high-foaming type; machinedishwashing agents, including the various tablet, granular, liquid andrinse-aid types for household and institutional use; liquid cleaning anddisinfecting agents, including antibacterial hand-wash types, cleaningbars, car or carpet shampoos, bathroom cleaners including toilet bowlcleaners; and metal cleaners, fabric conditioning products includingsoftening and/or freshing that may be in liquid, solid and/or dryersheet form; as well as cleaning auxiliaries such as bleach additives and“stain-stick” or pre-treat types, substrate-laden products such as dryeradded sheets, dry and wetted wipes and pads, nonwoven substrates, andsponges; as well as sprays and mists. All of such products which areapplicable may be in standard, concentrated or even highly concentratedform even to the extent that such products may in certain aspect benon-aqueous.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

As used herein, the term “situs” includes paper products, fabrics,garments, hard surfaces, hair and skin.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

High Efficiency Encapsulates and Slurry/Aggolmerates Comprising Same

An encapsulate that may comprise a core, a wall having an outer surfaceand a coating, said wall encapsulating said core, said coating coatingthe outer surface of said wall, said coating may comprise one or moreefficiency polymers having the following formula:

wherein:

-   -   a) wherein a and b may be integers or averages (real numbers)        from about 50-100,000;    -   b) each R1 may be independently selected from H, CH₃, (C═O)H,        alkylene, alkylene with unsaturated C—C bonds, CH₂—CROH,        (C═O)—NH—R, (C═O)—(CH₂)_(n)—OH, (C═O)—R, (CH₂)_(n)-E,        —(CH₂—CH(C═O))_(n)—XR, —(CH₂)_(n)—COOH, —(CH₂)_(n)—NH₂,        —CH₂)_(n)—(C═O)NH₂, the index n may be a integer from about 0 to        about 24, E may be an electrophilic group; R may be a saturated        or unsaturated alkane, dialkylsiloxy, dialkyloxy, aryl,        alkylated aryl, that may further contain a moiety selected from        the group consisting of cyano, OH, COOH, NH₂, NHR, sulfonate,        sulphate, —NH₂, quaternized amines, thiols, aldehyde, alkoxy,        pyrrolidone, pyridine, imidazol, imidazolinium halide,        guanidine, phosphate, monosaccharide, oligo or polysaccharide;    -   c) R2 or R3 can be absent or present:        -   (i) when R3 is present each R2 may be independently selected            from the group consisting of —NH₂, —COO—, —(C═O)—, —O—, —S—,            —NH—(C═O)—, —NR₁—, dialkylsiloxy, dialkyloxy, phenylene,            naphthalene, alkyleneoxy; and each R3 may be independently            selected the same group as R1;        -   (ii) when R3 is absent each R2 may be independently selected            from the group consisting of —NH₂, —COO—, —(C═O)—, —O—, —S—,            —NH—(C═O)—, —NR₁—, dialkylsiloxy, dialkyloxy, phenylene,            naphthalene, alkyleneoxy; and each R3 may be independently            selected the same group as R1; and        -   (iii) when R2 is absent, each R3 may be independently            selected the same group as R1;    -   d) said one or more efficiency polymers having an average        molecular mass from about 1,000 Da to about 50,000,000 Da, from        about 5,000 Da, to about 25,000,000 Da, from about 10,000 Da to        about 10,000,000 Da, or even from about 340,000 Da to about        1,500,000 Da; a hydrolysis degree, for polyvinyl formamides, of        from about 5% to about 95%, from about 7% to about 60%, or even        from about 10% to about 40%; and/or a charge density from about        1 meq/g efficiency polymer to about 23 meq/g efficiency polymer,        from about 1.2 meq/g efficiency polymer and 16 meq/g efficiency        polymer, from about 2 meq/g efficiency polymer to about 10 meq/g        efficiency polymer, or even from about 1 meq/g efficiency        polymer to about 4 meq/g efficiency polymer

is disclosed.

In one aspect of said encapsulate, one or more efficiency polymers isselected from the group consisting of polyvinyl amines, polyvinylformamides, and polyallyl amines and copolymers thereof, said one ormore efficiency polymers may have:

-   -   a) an average molecular mass from about 1,000 Da to about        50,000,000 Da, from about 5,000 Da, to about 25,000,000 Da, from        about 10,000 Da to about 10,000,000 Da, or even from about        340,000 Da to about 1,500,000 Da;    -   b) a hydrolysis degree, for said polyvinyl formamides, of from        about 5% to about 95%, from about 7% to about 60%, or even from        about 10% to about 40%; and/or    -   c) a charge density from about 1 meq/g efficiency polymer to        about 23 meq/g efficiency polymer, from about 1.2 meq/g        efficiency polymer and 16 meq/g efficiency polymer, from about 2        meq/g efficiency polymer to about 10 meq/g efficiency polymer,        or even from about 1 meq/g efficiency polymer to about 4 meq/g        efficiency polymer.

In one aspect of said encapsulate, said coating may comprise one or morepolyvinyl formamides said polyvinyl formamides that may have:

-   -   a) an average molecular mass from about 1,000 Da to about        50,000,000 Da, from about 5,000 Da, to about 25,000,000 Da, from        about 10,000 Da to about 10,000,000 Da, or even from about        340,000 Da to about 1,500,000 Da;    -   b) a hydrolysis degree, for said polyvinyl formamides, of from        about 5% to about 95%, from about 7% to about 60%, or even from        about 10% to about 40%; and    -   c) a charge density from about 1 meq/g efficiency polymer to        about 23 meq/g efficiency polymer, from about 1.2 meq/g        efficiency polymer and 16 meq/g efficiency polymer, from about 2        meq/g efficiency polymer to about 10 meq/g efficiency polymer,        or even from about 1 meq/g efficiency polymer to about 4 meq/g        efficiency polymer. In the aforementioned aspect, efficiency        polymer is synonymous with polyvinyl formamide.

In one aspect of said encapsulate, said encapsulate may have a coatingto wall ratio of from about 1:200 to about 1:2, from about 1:100 toabout 1:4, or even from about 1:80 to about 1:10.

In one aspect of said encapsulate;

-   -   a) said core may comprise a material selected from the group        consisting of perfumes; brighteners; dyes; insect repellants;        silicones; waxes; flavors; vitamins; fabric softening agents;        skin care agents in one aspect, paraffins; enzymes;        anti-bacterial agents; bleaches; sensates; and mixtures thereof;    -   b) said wall may comprise a material selected from the group        consisting of polyethylenes; polyamides; polystyrenes;        polyisoprenes; polycarbonates; polyesters; polyacrylates;        aminoplasts, in one aspect said aminoplast may comprise a        polyureas, polyurethane, and/or polyureaurethane, in one aspect        said polyurea may comprise polyoxymethyleneurea and/or melamine        formaldehyde; polyolefins; polysaccharides, in one aspect        alginate and/or chitosan; gelatin; shellac; epoxy resins; vinyl        polymers; water insoluble inorganics; silicone; and mixtures        thereof.

In one aspect of said encapsulate, said core may comprise perfume andsaid wall may comprise melamine formaldehyde and/or cross linkedmelamine formaldehyde.

In one aspect of said encapsulate, said core may comprise perfume andsaid wall may comprise melamine formaldehyde and/or cross linkedmelamine formaldehyde, poly(acrylic acid) and poly(acrylic acid-co-butylacrylate).

In one aspect of said encapsulate, said encapsulate may comprise aperfume that may comprise one or more perfume raw materials thatprovides improved perfume performance under high soil conditions and incold water. Suitable perfume materials can be found in US publishedpatent applications 2008/0031961A1 and 2008/0994454A1. A non-limitinglist of such perfume raw materials are disclosed in Table 1 below.

TABLE 1 Useful Perfume Raw Materials Item Common Name IUPAC Name 1Methyl 2-methyl butyrate methyl 2-methylbutanoate 2 Isopropyl 2-methylbutyrate propan-2-yl 2-methylbutanoate 3 Ethyl-2 Methyl Butyrate ethyl2-methylbutanoate 4 Ethyl-2 Methyl Pentanoate ethyl 2-methylpentanoate 5Ethyl heptanoate ethyl heptanoate 6 Ethyl octanoate Ethyl octanoate 7isobutyl hexanoate 2-methylpropyl hexanoate 8 Amyl butyrate pentylbutanoate 9 Amyl heptanoate Pentyl heptanoate 10 Isoamyl isobutyrate3-methylbutyl 2-methylpropanoate 11 Hexyl acetate hexyl acetate 12 hexylbutyrate hexyl butanoate 13 hexyl isobutyrate hexyl 2-methylpropanoate14 hexyl isovalerate hexyl 3-methylbutanoate 15 hexyl propionate hexylpropanoate 16 Ethyl 2-cyclohexyl propanoate ethyl 2-cyclohexylpropanoate17 Ethyl 3,5,5-trimethyl hexanoate ethyl 3,5,5-trimethylhexanoate 18glyceryl 5-hydroxydecanoate 2,3-dihydroxypropyl 5-hydroxydecanoate 19Prenyl acetate 3-methyl 2-butenyl acetate 20 3-methyl 2-butenyl acetate3-methyl 2-butenyl acetate 21 methyl 3-nonenoate methyl non-3-enoate 22Ethyl (E)-dec-4-enoate Ethyl (E)-dec-4-enoate 23 Ethyl (E)-oct-2-enoateEthyl (E)-oct-2-enoate 24 Ethyl 2,4-decadienoate ethyl(2E,4Z)-deca-2,4-dienoate 25 Ethyl 3-octenoate ethyl (E)-oct-3-enoate 26Citronellyl acetate 3,7-dimethyloct-6-enyl acetate 27 Ethyltrans-2-decenoate ethyl (E)-dec-2-enoate 28 2-hexen-1-yl isovalerate[(E)-hex-2-enyl] acetate 29 2-hexen-1-yl propionate [(E)-hex-2-enyl]propanoate 30 2-hexen-1-yl valerate [(E)-hex-2-enyl] pentanoate 313-hexen-1-yl (E)-2-hexenoate [(Z)-hex-3-enyl] (E)-hex-2-enoate 323-Hexen-1-yl 2-methyl butyrate [(Z)-hex-3-enyl] 2-methylbutanoate 333-hexen-1-yl acetate [(Z)-hex-3-enyl] acetate 34 3-hexen-1-yl benzoate[(Z)-hex-3-enyl] benzoate 35 3-hexen-1-yl formate [(Z)-hex-3-enyl]formate 36 3-hexen-1-yl tiglate [(Z)-hex-3-enyl] (Z)-2-methylbut-2-enoate 37 2-methyl butyl 2-methyl butyrate 2-methylbutyl2-methylbutanoate 38 Butyl isovalerate butyl 3-methylbutanoate 39Geranyl acetate [(2E)-3,7-dimethylocta-2,6-dienyl] acetate 40 Geranylbutyrate [(2E)-3,7-dimethylocta-2,6-dienyl] butanoate 41 Geranylisovalerate [(3E)-3,7-dimethylocta-3,6-dienyl] 3- methylbutanoate 42Geranyl propionate [(2E)-3,7-dimethylocta-2,6-dienyl] propanoate 43Allyl cyclohexane acetate prop-2-enyl 2-cyclohexylacetate 44 AllylCyclohexyl Propionate prop-2-enyl 3-cyclohexylpropanoate 45 allylcyclohexyl valerate prop-2-enyl 5-cyclohexylpentanoate 46 benzyloctanoate benzyl octanoate 47 cocolactone6-pentyl-5,6-dihydropyran-2-one 48 coconut decanone8-methyl-1-oxaspiro(4.5)decan-2-one 49 gamma undecalactone5-heptyloxolan-2-one 50 gamma-decalactone 5-hexyloxolan-2-one 51gamma-dodecalactone 5-octyloxolan-2-one 52 jasmin lactone6-[(E)-pent-2-enyl]oxan-2-one 53 Jasmolactone5-[(Z)-hex-3-enyl]oxolan-2-one 54 Nonalactone 6-butyloxan-2-one 556-acetoxydihydrotheaspirane [2a,5a(S*)]-2,6,10,10-tetramethyl-1-oxaspiro[4.5]decan-6-yl acetate 56 Phenoxyethyl isobutyrate2-(phenoxy)ethyl 2-methylpropanoate 57 Pivacyclene 58 Verdox(2-tert-butylcyclohexyl) acetate 59 cyclobutanate3a,4,5,6,7,7a-hexahydro-4,7-methano-1g- inden-5(or 6)-yl butyrate 60Dimethyl Anthranilate methyl 2-methylaminobenzoate 61 Methyl Antranilatemethyl 2-aminobenzoate 62 Octyl Aldehyde Octanal 63 Nonanal Nonanal 64Decyl aldehyde Decanal 65 Lauric Aldehyde Dodecanal 66 Methyl NonylAcetaldehyde 2-methyl undecanal 67 Methyl Octyl Acetaldehyde 2-methyldecanal 68 2,4-Hexadienal (2E,4E)-hexa-2,4-dienal 69 Intreleven Aldehydeundec-10-enal 70 Decen-1-al (E)-dec-2-enal 71 Nonen-1-al(E)-2-nonen-1-al 72 Adoxal 2,6,10-trimethylundec-9-enal 73 Geraldehyde(4Z)-5,9-dimethyldeca-4,8-dienal 74 Iso cyclo citral2,4,6-trimethylcyclohex-3-ene-1- carbaldehyde 75 d-limonene mainly1-methyl-4-prop-1-en-2-yl-cyclohexene 76 Ligustral2,4-dimethylcyclohex-3-ene-1- carbaldehyde 77 Myrac aldehyde4-(4-methylpent-3-enyl)cyclohex-3-ene-1- carbaldehyde 78 Tridecenaltridec-2-enal 79 Triplal 2,4-dimethyl-3-cyclohexene-1- carboxaldehyde 80Vertoliff 1,2-dimethylcyclohex-3-ene-1- carbaldehyde 81 Cyclal C2,4-dimethylcyclohex-3-ene-1- carbaldehyde 82 Anisic aldehyde4-methoxybenzaldehyde 83 Helional 3-(1,3-benzodioxol-5-yl)-2-methylpropanal 84 Heliotropin 1,3-benzodioxole-5-carbaldehyde 85Neocaspirene 86 Beta Naphthol Ethyl Ether 2-ethoxynaphtalene 87 BetaNaphthol Methyl Ether 2-methoxynaphtalene 88 hyacinth ether2-cyclohexyloxyethylbenzene 89 2-heptyl cyclopentanone (fleuramone)2-heptylcyclopentan-1-one 90 menthone-8-thioacetateO-[2-[(1S)-4-methyl-2- oxocyclohexyl]propan-2-yl] ethanethioate 91Nectaryl 2-[2-(4-methyl-1-cyclohex-3- enyl)propyl]cyclopentan-1-one 92Phenyl Naphthyl Ketone naphthalen-2-yl-phenylmethanone 93 decen-1-ylcyclopentanone 2-[(2E)-3,7-dimethylocta-2,6-dienyl] cyclopentan-1-one 94fruity cyclopentanone (veloutone)2,2,5-trimethyl-5-pentylcyclopentan-1-one 95 4-methoxy-2-methyl butanethiol 4-methoxy-2-methylbutane-2-thiol (blackcurrant mercaptan) 96Grapefruit Mercaptan 2-(4-methyl-1-cyclohex-3-enyl)propane- 2-thiol 97Buccoxime N-(1,5-dimethyl-8- bicyclo[3.2.1]octanylidene)hydroxylamine 98Labienoxime 2,4,4,7-Tetramethyl-6,8-nonadiene-3-one oxime 99Undecavertol (E)-4-methyldec-3-en-5-ol 100 Decanal diethyl acetal1,1-diethoxydecane 101 Diethyl maleate diethyl but-2-enedioate 102 EthylAcetoacetate ethyl 3-oxobutanoate 103 frutonile 2-Methyldecanenitrile104 Methyl dioxolan ethyl 2-(2-methyl-1,3-dioxolan-2- yl)acetate 105Cetalox 3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran 106 Cyclopentol 107 Delta-damascone(E)-1-(2,6,6-trimethyl-1-cyclohex-3- enyl)but-2-en-1-one 108 Eucalyptol1,3,3-trimethyl-2-oxabicyclo[2,2,2]octane 109 Flor acetate 110 Iononegamma methyl (E)-3-methyl-4-(2,6,6-trimethyl-1-cyclohex-2-enyl)but-3-en-2-one 111 Laevo trisandol 112 Linalool3,7-dimethylocta-1,6-dien-3-ol 113 Violiff [(4Z)-1-cyclooct-4-enyl]methyl carbonate 114 Cymal 3-(4-propan-2-ylphenyl)butanal 115 Bourgeonal3-(4-tert-butylphenyl)propanal

The perfume microcapsules may be contained in a perfume microcapsuleslurry.

In the context of the present invention, a perfume microcapsule slurryis defined as a watery dispersion, containing from 10% to 50% by weightof the slurry of perfume microcapsules. The perfume microcapsule slurrymay comprise at least 20%, more preferably at least 40%, by weight ofthe perfume microcapsule slurry of encapsulated perfume ingredients

The perfume microcapsule slurry of the present invention may comprise awater-soluble salt, which is present as a residual impurity of theperfume microcapsule slurry. This residual impurity could be from otheringredients in the perfume microcapsule slurry, which are purchased fromvarious suppliers. In one aspect, the perfume microcapsule slurry ispurchased from a supplier. The supplier may add additional water-solublesalt to the perfume microcapsule slurry to adjust the rheology profilesof the perfume microcapsule slurries, to improve the stability of theslurry during transport and long-term storage.

In the context of the present invention, water-soluble salts herein meanwater-soluble ionic compounds, composed of dissociated positivelycharged cations and negatively charged anions. In the context of thepresent invention, “water-soluble” can be defined as a solubility indemineralised water at ambient temperature and atmospheric pressure. Theperfume microcapsule slurry may comprise from 1 mmol/kg to 750 mmol/kgof water-soluble salt. In another embodiment, the perfume microcapsuleslurry may comprise from 10 mmol/kg to 750 mmol/kg of water-solublesalt. In yet another embodiment, the perfume microcapsule slurry maycomprise from 1 to 265 mmol/kg of water-soluble salt.

In one aspect the water-soluble salts present in the perfumemicrocapsule slurry are formed of polyvalent cations selected from thegroup comprising alkaline earthmetals, transition metals or metals,together with suitable monoatomic or polyatomic anions. In anotherembodiment, the water-soluble salt comprises cations, the cations beingselected from the group comprising Beryllium, Magnesium, Calcium,Strontium, Barium, Scandium, Titan, Iron, Copper, Aluminium, Zinc,Germanium, Tin. In another embodiment, the water-soluble salt comprisesanions, the anions being selected from the group comprising Fluorine,Chlorine, Bromine, Iodine, Acetate, Carbonate, Citrate, hydroxide,Nitrate, Phosphite, phosphate and sulfate. In one embodiment, the anionsare the monoatomic anions of the halogens.

In addition to the encapsulates disclosed herein, a slurry that maycomprise a efficiency polymer coated encapsulate, wherein said slurrymay have zeta potential of from about −10 meV to about +50 meV,preferably from about +2 meV to about +40 meV, more preferably fromabout +5 meV to about +25 meV or from about −40 meV to about +35 meV,preferably from about −38 meV to about +25 meV, more preferably fromabout −35 meV to about +10 meV is disclosed. In one aspect, said slurrymay obtain the suitable level of the efficiency polymer as a result theefficiency polymer that is part of the encapsulate and/or theencapsulate comprising the efficiency polymer may be made via combiningan slurry comprising encapsulate with one or more efficiency polymers

In addition to the encapsulates disclosed herein, a slurry that maycomprise, based on total slurry weight, a sufficient amount ofefficiency polymer coated encapsulates to provide said slurry with fromabout 0.05% to about 10%, from about 0.1% to about 5%, from about 0.125%to about 2% of a efficiency polymer.

In one aspect, a slurry that may comprise, based total slurry weight,from about 0.01% to about 5%, from about 0.05% to about 2% or even fromabout 0.1% to about 1% of a polyvinyl formamide, from about 0% to about5% MgCl₂, from about 0.1 to about 3% MgCl₂ from about 0.2% to about 2.5%MgCl₂ from about 0% to about 1% Xanthan gum, from about 0.05% to about0.5%, from about 0.1% to about 0.25% Xanthan gum and one or more of thecoated or uncoated encapsules is disclosed,

In one aspect of said slurry, said polyvinyl formamide may have:

-   -   a) an average molecular mass from about 1,000 Da to about        50,000,000 Da, from about 5,000 Da, to about 25,000,000 Da, from        about 10,000 Da to about 10,000,000 Da, or even from about        340,000 Da to about 1,500,000 Da;    -   b) a hydrolysis degree, for said polyvinyl formamides, of from        about 5% to about 95%, from about 7% to about 60%, or even from        about 10% to about 40%; and    -   c) a charge density from about 1 meq/g polyvinyl formamide to        about 23 meq/g polyvinyl formamide, from about 1.2 meq/g        polyvinyl formamide and 16 meq/g polyvinyl formamide, from about        2 meq/g polyvinyl formamide to about 10 meq/g polyvinyl        formamide, or even from about 1 meq/g polyvinyl formamide to        about 4 meq/g polyvinyl formamide.

In one aspect, a process of making an improved slurry comprisingcombining, in any order, an encapsulate, a efficiency and optionally astabilization system and optionally a biocide is disclosed. In oneaspect, said efficiency polymer may comprise polyvinyl formamide, saidsrablization system may comprise MgCl₂ and xanthan gum.

In one aspect of said process of making an improved slurry, saidencapsulate and said efficiency are permitted to be in intimate contactfor at least 15 minutes, for at least 1 hour, or even for at 4 hoursbefore said slurry is used in a product or used to produce anagglomerate.

In one aspect, any of the encapsulates and/or slurries disclosed hereinmay be used to produce an agglomerate.

In one aspect, a process of making the agglomerate said processcomprising:

-   -   a) combining an encapsulate and/or slurry; a plasticizer, in one        aspect, a plasticizer comprising water; and, optionally, a        binder and/or chelant to form a mixture;    -   b) combining said mixture with said dusting agent, in one        aspect, a dusting agent that comprises silica, to form a        material; and    -   c) removing a sufficient amount of said plasticizer from said        material to yield a product comprising, based on total product        weight from 1% to 50% plasticizer.

In one aspect, said plasticizer comprises water.

Suitable capsules that can be turned into the high efficiency capsulesdisclosed herein can be made in accordance with Applicants' teachingincluding but not limited to Applicants' examples, the teaching of USPA2008/0305982 A1 and/or USPA 2009/0247449 A1. Alternatively, suitablecapsules can be purchased from Appleton Papers Inc. of Appleton, Wis.USA.

In addition, the materials for making the aforementioned encapsulatescan be obtained from CP Kelco Corp. of San Diego, Calif., USA; BASF AGof Ludwigshafen, Germany; Rhodia Corp. of Cranbury, N.J., USA; HerculesCorp. of Wilmington, Del., USA; Agrium Inc. of Calgary, Alberta, Canada,ISP of New Jersey U.S.A., Akzo Nobel of Chicago, Ill., USA; StroeverShellac Bremen of Bremen, Germany; Dow Chemical Company of Midland,Mich., USA; Bayer AG of Leverkusen, Germany; Sigma-Aldrich Corp., St.Louis, Mo., USA.

Suitable efficiency polymers such as polyvinylamide-polyvinylaminecopolymers can be produced by selective hydrolization of thepolyvinylformamide starting polymer.

Suitable efficiency polymers can also be formed by copolymerisation ofvinylformamide with arcylamide, acrylic acid, acrylonitrile, ethylene,sodium acrylate, methyl acrylate, maleic anhydride, vinyl acetate,n-vinylpyrrolidine.

Suitable efficiency polymers or oligomers can also be formed by cationicpolymerisation of vinylformamide with protonic acids, such asmethylsulfonic acid, and or Lewis acids, such as boron trifluoride.

Suitable efficiency polymers can be obtained from BASF AG ofLudwigshafen, Germany and include Lupamin® 9010 and Lupamin® 9030.

Process of Making Encapsulates Having Coating

In one aspect, a process of making a coated encapsulate comprisingcombining an encapsulate, and a one or more efficiency polymers isdisclosed.

In one aspect, a process of making a coated encapsulate wherein saidencapsulate, when combined with said one or more efficiency polymers, iscontained in a slurry is disclosed.

In one aspect, a process of making a coated encapsulate wherein asufficient amount of efficiency polymer is combined with said slurry toprovide said slurry with, based on total slurry weight, from about 0.05%to about 10%, from about 0.1% to about 5%, or even from about 0.125% toabout 2% of said efficiency polymer is disclosed.

The high efficiency polymers used in making the aforementioned coatedencapsulates may be the efficiency polymers described in the HighEfficiency Encapsulates and Slurry/Aggolmerates Comprising Same sectionof the present specification.

Consumer Product

In one aspect, a consumer product comprising any of the encapsulates,agglomerate comprising such encapsulates and/or slurries disclosedherein is disclosed.

In one aspect of said consumer product, said consumer product may be acleaning and/or treatment composition.

In one aspect of said consumer product, said consumer product may be alaundry detergent and/or fabric softener.

In one aspect of said consumer product, said consumer product may be afluid laundry detergent. Said fluid laundry detergent may, in oneaspect, comprise, based on total fluid laundry detergent weight, fromabout 3% to about 80%, from about 3% to about 70%, from about 5% toabout 60%, or even from about 8% to about 50% water,

In one aspect of said fluid detergent, said fluid detergent may be aliquid laundry detergent.

In one aspect of said consumer product, said consumer product may be afluid fabric softener. Said fluid fabric softener may, in one aspect,comprise, based on total fluid fabric softener weight, from about 30% toabout 90%, from about 55% to about 90%, from about 65% to about 85%, oreven from about 70% to about 85% water.

In one aspect of said fluid fabric softener, said fluid fabric softenermay be a liquid fabric softener.

In one aspect of said consumer product, said consumer product may besolid detergent and an adjunct ingredient.

In one aspect of said consumer product, said consumer product may be afluid beauty care product, for example a shampoo. Said fluid beauty careproduct may, in one aspect, comprise, based on total fluid beauty careproduct weight, from about 30% to about 95%, from about 55% to about90%, or even from about 65% to about 85% water.

In one aspect of said consumer product, said consumer product may be aconditioner.

In one aspect, said consumer product may comprise a sufficient amount ofslurry and/or encapsulate to provide said consumer product with anefficiency polymer level, based on total consumer product weight, offrom about 0.0001% to about 0.1%, about 0.001% to about 0.1%, or evenfrom about 0.001% to about 0.05%.

In one aspect, said consumer product may comprise a material selectedfrom the group consisting of an anionic surfactant, cationic surfactant,silicone and mixtures thereof, said consumer product may also have:

-   -   a) an anionic surfactant to efficiency polymer ratio of from        about 100.000:1 to about 1:1, from about 25.000:1 to about 10:1,        or even from about 10.000:1 to about 100:1;    -   b) a cationic surfactant to efficiency polymer ratio of from        about 100.000:1 to about 1:1, from about 25.000:1 to about 10:1,        or even from about 10.000:1 to about 100:1; and/or    -   c) a silicone to efficiency polymer ratio of from about        100.000:1 to about 1:1 from about 25.000:1 to about 10:1, or        even from about 10.000:1 to about 100:1.

In one aspect, the encapsulates disclosed herein are suitable for use inconsumer products, cleaning and treatment compositions and fabric andhard surface cleaning and/or treatment compositions, detergents, andhighly compacted consumer products, including highly compacted fabricand hard surface cleaning and/or treatment compositions, for examplehighly compacted detergents that may be solids or fluids, at levels,based on total consumer product weight, from about 0.001% to about 20%,from about 0.01% to about 10%, from about 0.05% to about 5%, from about0.1% to about 2%.

In one aspect, a consumer product comprising an adjunct ingredientselected from the group consisting of polymers, in one aspect, acationic polymer, surfactants, builders, chelating agents, opticalbrighteners, dye transfer inhibiting agents, dispersants, enzymes,enzyme stabilizers, catalytic materials, bleach activators, polymericdispersing agents, clay soil removal/anti-redeposition agents,brighteners, dye polymer conjugates; dye clay conjugates, sudssuppressors, dyes, bleach catalysts, additional perfume and/or perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids, rheology modifiers,structurants, thickeners, pigments, water and mixtures thereof isdisclosed.

In one aspect, a consumer product comprising an adjunct ingredientcomprising a rheology modifier, thickener and/or structurant having ahigh shear viscosity, at 20 sec-1 shear rate and at 21° C., of from 1 to7000 cps and a viscosity at low shear (0.5 sec-1 shear rate at 21° C.)of greater than 1000 cps, or even 1000 cps to 200,000 cps. In oneaspect, for cleaning and treatment compositions, such rheology modifiersimpart to the aqueous liquid composition a high shear viscosity, at 20sec-1 and at 21° C., of from 50 to 3000 cps and a viscosity at low shear(0.5 sec-1 shear rate at 21° C.) of greater than 1000 cps, or even 1000cps to 200,000 cps. In one aspect, suitable rheology modifiers,thickeners and/or structurants may be selected from the group consistingof polyacrylates, quaternized polyacrylates, polymethacrylates,polyamides, quaternized polymethacrylates, polycarboxylates, polymericgums like pectine, alginate, arabinogalactan (gum Arabic), carrageenan,gellan gum, xanthan gum and guar gum, other non-gum polysaccharides likegellan gum, and combinations of these polymeric materials,hydroxyl-containing fatty acids, fatty esters or fatty waxes, castor oiland its derivatives, hydrogenated castor oil derivatives such ashydrogenated castor oil and hydrogenated castor wax; and mixturesthereof.

In one aspect, a consumer product said consumer product being a fluiddetergent and comprising, based on total fluid detergent weight, lessthen about 80% water, less than about 60% to about 2% water, from about45% to about 7% water, from about 35% to about 9% water is disclosed.

In addition to the encapsulates disclosed herein, certain perfumedelivery systems may be used in the aforementioned compositions and/orconsumer products. Methods of making such perfume delivery systems andmethods of making such perfume delivery systems are disclosed in USPA2007/0275866 A1. Such perfume delivery systems include: Polymer AssistedDelivery (PAD), Molecule-Assisted Delivery (MAD), Fiber-AssistedDelivery (FAD), Amine Assisted Delivery (AAD), Cyclodextrin DeliverySystem (CD), Starch Encapsulated Accord (SEA), Inorganic CarrierDelivery System (ZIC), Pro-Perfume (PP). Such perfume delivery systemsmay be used in any combination in any type of consumer product, cleaningand/or treatment composition, fabric and hard surface cleaning and/ortreatment composition, detergent, and highly compact detergent.

Perfume Microcapsule

It is advantageous to add perfume in the form of encapsulated perfumeingredients to a composition, as the encapsulation of the perfumeingredients allows a controlled and eventually targeted release of theperfume ingredients. Perfume ingredients, are the individual chemicalcompounds that are used to make a perfume composition. A perfumecomposition comprises one or more perfume ingredients, the choice oftype and number of ingredients being dependent upon the final desiredscent. The present invention may comprise perfume microcapsules. It iswell known to those skilled in the art, that perfume microcapsulesrelease perfume ingredients during handling of fabrics and during the inwear process, providing improved longer lasting freshness on fabrics, ascompared to the addition of neat perfume alone. The release of theperfume ingredients is triggered by mechanical stress breaking thecapsule wall and allowing the diffusion of the encapsulated perfumeingredient.

A perfume microcapsule comprises a capsule surrounding a core, that corecomprising perfume ingredients. The capsule can be made of a number ofmaterials, but most preferred is cross-linked melamine formaldehyde. Thecapsule wall material may comprise a suitable resin including thereaction product of an aldehyde and an amine, suitable aldehydesinclude, formaldehyde. Suitable amines can include those selected fromthe group comprising melamine, urea, benzoguanamine, glycoluril, andmixtures thereof. Suitable melamines can include those selected from thegroup comprising methylol melamine, methylated methylol melamine, iminomelamine and mixtures thereof. Suitable ureas can include those selectedfrom the group comprising dimethylol urea, methylated dimethylol urea,urea-resorcinol, and mixtures thereof.

In the context of the present invention, any suitable perfume ingredientmay be used. Those skilled in the art will recognize suitable compatibleperfume ingredients for use in the perfume microcapsules, and will knowhow to select combinations of ingredients to achieve desired scents.

In one aspect, at least 75%, 85% or even 90% of said perfumemicrocapsules may have a particle size of from about 1 microns to about80 microns, about 5 microns to 60 microns, from about 10 microns toabout 50 microns, or even from about 15 microns to about 40 microns.

At least 75%, 85% or even 90% of said perfume microcapsules may have aparticle wall thickness of from about 60 nm to about 250 nm, from about80 nm to about 180 nm, or even from about 100 nm to about 160 nm.

The liquid fabric softening compositions of the present inventioncomprise from 0.05% to 0.8% by weight of the liquid fabric softeningcomposition of encapsulated perfume ingredients, present in the form ofa perfume microcapsule. This amount is necessary to ensure sufficientperfume is deposited onto the fabrics. Perfume and perfume microcapsulesare washed away during the laundry process. Therefore, it is importantto have enough perfume in the liquid fabric softening composition totake account of the inevitable loss, yet still have sufficientdeposition onto fabrics.

In one aspect, said perfume microcapsule may be spray dried.

Perfume Microcapsule Slurry and Agglomerate Adjunct Materials

For the purposes of the present invention, the non-limiting list ofadjuncts illustrated hereinafter are suitable for use in the instantcompositions and may be desirably incorporated in certain embodiments ofthe invention, for example to assist or enhance performance, fortreatment of the substrate to be cleaned, or to modify the aesthetics ofthe composition as is the case with perfumes, colorants, dyes or thelike. It is understood that such adjuncts are in addition to thecomponents that are supplied via Applicants' encapsulates, agglomeratesand/or slurries. The precise nature of these additional components, andlevels of incorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable adjunct materials include, but are not limited to, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic materials, bleach activators,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfume and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. In addition tothe disclosure below, suitable examples of such other adjuncts andlevels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and6,326,348 B1 that are incorporated by reference.

Each adjunct ingredients is not essential to Applicants' compositions.Thus, certain embodiments of Applicants' compositions do not contain oneor more of the following adjuncts materials: bleach activators,surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes,polymeric dispersing agents, clay and soil removal/anti-redepositionagents, brighteners, suds suppressors, dyes, additional perfumes andperfume delivery systems, structure elasticizing agents, fabricsofteners, carriers, hydrotropes, processing aids and/or pigments.However, when one or more adjuncts are present, such one or moreadjuncts may be present as detailed below:

Surfactants—The compositions according to the present invention cancomprise a surfactant or surfactant system wherein the surfactant can beselected from nonionic and/or anionic and/or cationic surfactants and/orampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.The surfactant is typically present at a level of from about 0.1%, fromabout 1%, or even from about 5% by weight of the cleaning compositionsto about 99.9%, to about 80%, to about 35%, or even to about 30% byweight of the cleaning compositions.

Builders—The compositions of the present invention can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds. ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more dye transfer inhibiting agents. Suitablepolymeric dye transfer inhibiting agents include, but are not limitedto, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Hueing Agents—Fluorescent optical brighteners emit at least some visiblelight. In contrast, fabric hueing agents can alter the tint of a surfaceas they absorb at least a portion of the visible light spectrum.Suitable fabric hueing agents include dyes, dye-clay conjugates.Suitable dyes include small molecule dyes and polymeric dyes. Suitablesmall molecule dyes include small molecule dyes selected from the groupconsisting of:

(1) Tris-Azo Direct Blue Dyes of the Formula

where at least two of the A, B and C napthyl rings are substituted by asulfonate group, the C ring may be substituted at the 5 position by anNH₂ or NHPh group, X is a benzyl or naphthyl ring substituted with up to2 sulfonate groups and may be substituted at the 2 position with an OHgroup and may also be substituted with an NH₂ or NHPh group.

(2) Bis-Azo Direct Violet Dyes of the Formula:

where Z is H or phenyl, the A ring is preferably substituted by a methyland methoxy group at the positions indicated by arrows, the A ring mayalso be a naphthyl ring, the Y group is a benzyl or naphthyl ring, whichis substituted by sulfate group and may be mono or disubstituted bymethyl groups.

(3) Blue or Red Acid Dyes of the Formula

where at least one of X and Y must be an aromatic group. In one aspect,both the aromatic groups may be a substituted benzyl or naphthyl group,which may be substituted with non water-solubilising groups such asalkyl or alkyloxy or aryloxy groups, X and Y may not be substituted withwater solubilising groups such as sulfonates or carboxylates. In anotheraspect, X is a nitro substituted benzyl group and Y is a benzyl group

(4) Red Acid Dyes of the Structure

where B is a naphthyl or benzyl group that may be substituted with nonwater solubilising groups such as alkyl or alkyloxy or aryloxy groups, Bmay not be substituted with water solubilising groups such as sulfonatesor carboxylates.

(5) Dis-Azo Dyes of the Structure

wherein X and Y, independently of one another, are each hydrogen, C₁-C₄alkyl or C₁-C₄-alkoxy, Rα is hydrogen or aryl, Z is C₁-C₄ alkyl;C₁-C₄-alkoxy; halogen; hydroxyl or carboxyl, n is 1 or 2 and m is 0, 1or 2, as well as corresponding salts thereof and mixtures thereof

(6) Triphenylmethane Dyes of the Following Structures

and mixtures thereof. In another aspect, suitable small molecule dyesinclude small molecule dyes listed below, certain of such dyes areselected from the group consisting of Colour Index (Society of Dyers andColourists, Bradford, UK). 1,4-Naphthalenedione,1-[2-[2-[4-[[4-(acetyloxy)butyl]ethylamino]-2-methylphenyl]diazenyl]-5-nitro-3-thienyl]-Ethanone,1-hydroxy-2-(1-naphthalenylazo)-Naphthalenedisulfonic acid, ion(2-),1-hydroxy-2-[[4-(phenylazo)phenyl]azo]-Naphthalenedisulfonic acid,ion(2-),2-[(1E)-[4-[bis(3-methoxy-3-oxopropyl)amino]-2-methylphenyl]azo]-5-nitro-3-Thiophenecarboxylicacid, ethyl ester,2-[[4-[(2-cyanoethyl)ethylamino]phenyl]azo]-5-(phenylazo)-3-Thiophenecarbonitrile,2-[2-[4-[(2-cyanoethyl)ethylamino]phenyl]diazenyl]-5-[2-(4-nitrophenyl)diazenyl]-3-Thiophenecarbonitrile,2-hydroxy-1-(1-naphthalenylazo)-Naphthalenedisulfonic acid, ion(2-),2-hydroxy-1-[[4-(phenylazo)phenyl]azo]-Naphthalenedisulfonic acid,ion(2-),4,4′-[[4-(dimethylamino)-2,5-cyclohexadien-1-ylidene]methylene]bis[N,N-dimethyl-Benzenamine,6-hydroxy-5-[(4-methoxyphenyl)azo]-2-Naphthalenesulfonic acid,monosodium salt, 6-hydroxy-5-[(4-methylphenyl)azo]-2-Naphthalenesulfonicacid, monosodium salt,7-hydroxy-8-[[4-(phenylazo)phenyl]azo]-1,3-Naphthalenedisulfonic acid,ion(2-),7-hydroxy-8-[2-(1-naphthalenyl)diazenyl]-1,3-Naphthalenedisulfonic acid,ion(2-),8-hydroxy-7-[2-(1-naphthalenyl)diazenyl]-1,3-Naphthalenedisulfonic acid,ion(2-),8-hydroxy-7-[2-[4-(2-phenyldiazenyl)phenyl]diazenyl]-1,3-Naphthalenedisulfonicacid, ion(2-), Acid Black 1, Acid black 24, Acid Blue 113, Acid Blue 15,Acid Blue 17, Acid Blue 25, Acid blue 29, Acid blue 3, Acid blue 40,Acid blue 45, Acid blue 62, Acid blue 7, Acid blue 75, Acid Blue 80,Acid Blue 83, Acid blue 9, Acid Blue 90, Acid green 27, Acid orange 12,Acid orange 7, Acid red 14, Acid red 150, Acid red 151, Acid red 17,Acid red 18, Acid red 266, Acid red 27, Acid red 4, Acid red 51, Acidred 52, Acid red 73, Acid red 87, Acid red 88, Acid red 92, Acid red 94,Acid red 97, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid violet43, Acid Violet 49, Basic blue 159, Basic blue 16, Basic blue 22, Basicblue 3, Basic blue 47, Basic blue 66, Basic blue 75, Basic blue 9, Basicviolet 1, Basic violet 2, Basic violet 3, Basic violet 4, Basic violet10, Basic violet 35, C.I. Acid black 1, C.I. Acid Blue 10, C.I. AcidBlue 113, C.I. Acid Blue 25, C.I. Acid Blue 29, C.I. Acid Blue 290 C.I.Acid Red 103, C.I. Acid red 150, C.I. Acid red 52, C.I. Acid red 73,C.I. Acid red 88, C.I. Acid red 91, C.I. Acid violet 17, C.I. Acidviolet 43, C.I. Direct Blue 1, C.I. Direct Blue 120, C.I. Direct Blue34, C.I. Direct Blue 70, C.I. Direct Blue 71, C.I. Direct Blue 72, C.I.Direct Blue 82, C.I. Direct violet 51, C.I. Disperse Blue 10, C.I.Disperse Blue 100, C.I. Disperse Blue 101, C.I. Disperse Blue 102, C.I.Disperse Blue 106:1, C.I. Disperse Blue 11, C.I. Disperse Blue 12, C.I.Disperse Blue 121, C.I. Disperse Blue 122, C.I. Disperse Blue 124, C.I.Disperse Blue 125, C.I. Disperse Blue 128, C.I. Disperse Blue 130, C.I.Disperse Blue 133, C.I. Disperse Blue 137, C.I. Disperse Blue 138, C.I.Disperse Blue 139, C.I. Disperse Blue 142, C.I. Disperse Blue 146, C.I.Disperse Blue 148, C.I. Disperse Blue 149, C.I. Disperse Blue 165, C.I.Disperse Blue 165:1, C.I. Disperse Blue 165:2, C.I. Disperse Blue 165:3,C.I. Disperse Blue 171, C.I. Disperse Blue 173, C.I. Disperse Blue 174,C.I. Disperse Blue 175, C.I. Disperse Blue 177, C.I. Disperse Blue 183,C.I. Disperse Blue 187, C.I. Disperse Blue 189, C.I. Disperse Blue 193,C.I. Disperse Blue 194, C.I. Disperse Blue 200, C.I. Disperse Blue 201,C.I. Disperse Blue 202, C.I. Disperse Blue 205, C.I. Disperse Blue 206,C.I. Disperse Blue 207, C.I. Disperse Blue 209, C.I. Disperse Blue 21,C.I. Disperse Blue 210, C.I. Disperse Blue 211, C.I. Disperse Blue 212,C.I. Disperse Blue 219, C.I. Disperse Blue 220, C.I. Disperse Blue 222,C.I. Disperse Blue 224, C.I. Disperse Blue 225, C.I. Disperse Blue 248,C.I. Disperse Blue 252, C.I. Disperse Blue 253, C.I. Disperse Blue 254,C.I. Disperse Blue 255, C.I. Disperse Blue 256, C.I. Disperse Blue 257,C.I. Disperse Blue 258, C.I. Disperse Blue 259, C.I. Disperse Blue 260,C.I. Disperse Blue 264, C.I. Disperse Blue 265, C.I. Disperse Blue 266,C.I. Disperse Blue 267, C.I. Disperse Blue 268, C.I. Disperse Blue 269,C.I. Disperse Blue 270, C.I. Disperse Blue 278, C.I. Disperse Blue 279,C.I. Disperse Blue 281, C.I. Disperse Blue 283, C.I. Disperse Blue 284,C.I. Disperse Blue 285, C.I. Disperse Blue 286, C.I. Disperse Blue 287,C.I. Disperse Blue 290, C.I. Disperse Blue 291, C.I. Disperse Blue 294,C.I. Disperse Blue 295, C.I. Disperse Blue 30, C.I. Disperse Blue 301,C.I. Disperse Blue 303, C.I. Disperse Blue 304, C.I. Disperse Blue 305,C.I. Disperse Blue 313, C.I. Disperse Blue 315, C.I. Disperse Blue 316,C.I. Disperse Blue 317, C.I. Disperse Blue 321, C.I. Disperse Blue 322,C.I. Disperse Blue 324, C.I. Disperse Blue 328, C.I. Disperse Blue 33,C.I. Disperse Blue 330, C.I. Disperse Blue 333, C.I. Disperse Blue 335,C.I. Disperse Blue 336, C.I. Disperse Blue 337, C.I. Disperse Blue 338,C.I. Disperse Blue 339, C.I. Disperse Blue 340, C.I. Disperse Blue 341,C.I. Disperse Blue 342, C.I. Disperse Blue 343, C.I. Disperse Blue 344,C.I. Disperse Blue 345, C.I. Disperse Blue 346, C.I. Disperse Blue 351,C.I. Disperse Blue 352, C.I. Disperse Blue 353, C.I. Disperse Blue 355,C.I. Disperse Blue 356, C.I. Disperse Blue 357 C.I. Disperse Blue 358,C.I. Disperse Blue 36, C.I. Disperse Blue 360, C.I. Disperse Blue 366,C.I. Disperse Blue 368, C.I. Disperse Blue 369, C.I. Disperse Blue 371,C.I. Disperse Blue 373, C.I. Disperse Blue 374, C.I. Disperse Blue 375,C.I. Disperse Blue 376, C.I. Disperse Blue 378, C.I. Disperse Blue 38,C.I. Disperse Blue 42, C.I. Disperse Blue 43, C.I. Disperse Blue 44,C.I. Disperse Blue 47, C.I. Disperse Blue 79, C.I. Disperse Blue 79:1,C.I. Disperse Blue 79:2, C.I. Disperse Blue 79:3, C.I. Disperse Blue 82,C.I. Disperse Blue 85, C.I. Disperse Blue 88, C.I. Disperse Blue 90,C.I. Disperse Blue 94, C.I. Disperse Blue 96, C.I. Disperse Violet 10,C.I. Disperse Violet 100, C.I. Disperse Violet 102, C.I. Disperse Violet103, C.I. Disperse Violet 104, C.I. Disperse Violet 106, C.I. DisperseViolet 107, C.I. Disperse Violet 12, C.I. Disperse Violet 13, C.I.Disperse Violet 16, C.I. Disperse Violet 2, C.I. Disperse Violet 24,C.I. Disperse Violet 25, C.I. Disperse Violet 3, C.I. Disperse Violet33, C.I. Disperse Violet 39, C.I. Disperse Violet 42, C.I. DisperseViolet 43, C.I. Disperse Violet 45, C.I. Disperse Violet 48, C.I.Disperse Violet 49, C.I. Disperse Violet 5, C.I. Disperse Violet 50,C.I. Disperse Violet 53, C.I. Disperse Violet 54, C.I. Disperse Violet55, C.I. Disperse Violet 58, C.I. Disperse Violet 6, C.I. DisperseViolet 60, C.I. Disperse Violet 63, C.I. Disperse Violet 66, C.I.Disperse Violet 69, C.I. Disperse Violet 7, C.I. Disperse Violet 75,C.I. Disperse Violet 76, C.I. Disperse Violet 77, C.I. Disperse Violet82, C.I. Disperse Violet 86, C.I. Disperse Violet 88, C.I. DisperseViolet 9, C.I. Disperse Violet 91, C.I. Disperse Violet 92, C.I.Disperse Violet 93, C.I. Disperse Violet 93:1, C.I. Disperse Violet 94,C.I. Disperse Violet 95, C.I. Disperse Violet 96, C.I. Disperse Violet97, C.I. Disperse Violet 98, C.I. Disperse Violet 99, C.I. ReactiveBlack 5, C.I. Reactive Blue 19, C.I. Reactive Blue 4, C.I. Reactive Red2, C.I. Solvent Blue 43, C.I. Solvent Blue 43, C.I. Solvent Red 14, C.I.Acid black 24, C.I. Acid blue 113, C.I. Acid Blue 29, C.I. Direct violet7, C.I. Food Red 14, Dianix Violet CC, Direct blue 1, Direct Blue 71,Direct blue 75, Direct blue 78, Direct blue 80, Direct blue 279, Directviolet 11, Direct violet 31, Direct violet 35, Direct violet 48, Directviolet 5, Direct Violet 51, Direct violet 66, Direct violet 9, DisperseBlue 106, Disperse blue 148, Disperse blue 165, Disperse Blue 3,Disperse Blue 354, Disperse Blue 364, Disperse blue 367, Disperse Blue56, Disperse Blue 77, Disperse Blue 79, Disperse blue 79:1, Disperse Red1, Disperse Red 15, Disperse Violet 26, Disperse Violet 27, DisperseViolet 28, Disperse violet 63, Disperse violet 77, Eosin Y, Ethanol,2,2′-[[4(3,5-dinitro-2-thienyl)azo]phenyl]imino]bis-, diacetate (ester),Lumogen F Blue 650, Lumogen F Violet 570,N-[2-[2-(3-acetyl-5-nitro-2-thienyl)diazenyl]-5-(diethylamino)phenyl]-Acetamide,N-[2-[2-(4-chloro-3-cyano-5-formyl-2-thienyl)diazenyl]-5-(diethylamino)phenyl]-Acetamide,N-[5-[bis(2-methoxyethyl)amino]-2-[2-(5-nitro-2,1-benzisothiazol-3-yl)diazenyl]phenyl]-Acetamide,N-[5-[bis[2-(acetyloxy)ethyl]amino]-2-[(2-bromo-4,6-dinitrophenyl)azo]phenyl]-Acetamide,Naphthalimide, derivatives, Oil Black 860, Phloxine B, Pyrazole, RoseBengal, Sodium6-hydroxy-5-(4-isopropylphenylazo)-2-naphthalenesulfonate, Solvent Black3, Solvent Blue 14, Solvent Blue 35, Solvent Blue 58, Solvent Blue 59,Solvent Red 24, Solvent Violet 13, Solvent Violet 8, Sudan Red 380,Triphenylmethane, and Triphenylmethane, derivatives and mixturesthereof.

Additional suitable hueing agents include, but are not limited to,thiophenes and thiazoliums described below. Suitable thiophenes may becharacterized by the following structure:

Wherein R₁ and R₂ can independently be selected from:

-   -   a) [(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)H]    -   wherein R′ is selected from the group consisting of H, CH₃,        CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected        from the group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures        thereof; wherein x+y≦5; wherein y≧1; and wherein z=0 to 5;    -   b) R₁=alkyl, aryl or aryl alkyl and        R₂═[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)]    -   wherein R′ is selected from the group consisting of H, CH₃,        CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected        from the group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures        thereof; wherein x+y≦10; wherein y≧1; and wherein z=0 to 5;    -   c) R₁═[CH₂CH₂(OR₃)CH₂OR₄] and R₂═[CH₂CH₂(OR₃)CH₂OR₄]    -   wherein R₃ is selected from the group consisting of H,        (CH₂CH₂O)_(z)H, and mixtures thereof; and wherein z=0 to 10;    -   wherein R₄ is selected from the group consisting of        (C₁-C₁₆)alkyl, aryl groups, and mixtures thereof; and    -   d) wherein R1 and R2 can independently be selected from the        amino addition product of styrene oxide, glycidyl methyl ether,        isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl        glycidyl ether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl        ether, followed by the addition of from 1 to 10 alkylene oxide        units.

In one aspect, such thiophenes may be characterized by the followingstructure:

wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof; wherein R″ is selected fromthe group consisting of H, CH₂O(CH₂CH₂O)_(z)H, and mixtures thereof;wherein x+y≦5; wherein y≧1; and wherein z=0 to 5.

Suitable thiazolium dyes include azo dyes that may have Formula (I)below:

wherein:

-   -   R₃ and R₄ may be identical or different and, independently of        one another, are hydrogen, a saturated or unsaturated        (C₁-C₂₂)-alkyl group, a (C₁-C₂₂)-alkyl group substituted by a        halogen atom, a hydroxy-(C₂-C₂₂)-alkyl group optionally        interrupted by oxygen, a polyether group derived from ethylene        oxide, propylene oxide or butylene oxide, an        amino-(C₁-C₂₂)-alkyl group, a substituted or unsubstituted        phenyl group or a benzyl group, a (C₁-C₂₂)-alkyl group        terminated in sulfonate, sulfate, or carboxylate, or the radical        groups R₃ and R₄, together with the remaining molecule, can form        a heterocyclic or carbocyclic, saturated or unsaturated,        substituted or unsubstituted ring system optionally substituted        by halogen, sulfate, sulfonate, phosphate, nitrate, and        carboxylate;    -   X may be a radical group of the phenol series or a heterocyclic        radical group or aniline series or m-toluidine series that may        have Formula II below;

-   -   -   wherein:            -   R₅ and R₆ may be identical or different and,                independently of one another, are a straight or branched                saturated or unsaturated (C₁-C₂₂)-alkyl group, a                (C₁-C₂₂)-alkyl ether group, a hydroxy-(C₂-C₂₂)-alkyl                group optionally interrupted by oxygen, a polyether                group derived from ethylene oxide, propylene oxide,                butylene oxide, glycidyl or combinations thereof, an                amino-(C₁-C₂₂)-alkyl group, a substituted or                unsubstituted phenyl group or a benzyl group, a linear                or branched (C₁-C₂₂)-alkyl group terminated in a linear                or branched (C₁-C₂₂)-alkyl, hydroxyl, acetate,                sulfonate, sulfate, or carboxylate, group or R₅ and R₆                or R₅ and R₇ or R₆ and R₇, together with the nitrogen                atom, form a 5-membered to 6-membered ring system, which                may comprise a further heteroatom; or R₅ and R₆ or R₅                and R₇ or R₆ and R₇, form with a carbon atom of the                benzene ring an optionally oxygen-containing or nitrogen                containing five or six-membered heterocycle which may be                substituted with one or more (C₁-C₂₂)-alkyl group;            -   R₇ may be identical or different and, independently of                one another, are hydrogen, a halogen atom, a saturated                or unsaturated (C₁-C₂₂)-alkyl group, a (C₁-C₂₂)-alkyl                ether group, a hydroxyl group, a hydroxy-(C₁-C₂₂)-alkyl                group, a (C₁-C₂₂)-alkoxy group, a cyano group, a nitro                group, an amino group, a (C₁-C₂₂)-alkylamino group, a                (C₁-C₂₂)-dialkylamino group, a carboxylic acid group, a                C(O)0-(C₁-C₂₂)-alkyl group, a substituted or                unsubstituted C(O)0-phenyl group;

    -   Q⁻ may be an anion that balances the overall charge of the        compound of Formula I, and the index q may be either 0 or 1.        Suitable anions include chloro, bromo, methosulfate,        tetrafluoroborate, and acetate anions.

    -   R₁ may be a (C₁-C₂₂)-alkyl, an alkyl aromatic or an alkyl        sulfonate radical having Formula (III) below;

-   -   -   wherein            -   R₂ is hydrogen, methyl, ethyl, propyl, acetate or a                hydroxyl group; m and p are integers from 0 to (n−1), n                is an integer from 1 to 6 and m+p=(n−1);                with the proviso that the heterocycle of the Formula (I)                comprises at least two and at most three heteroatoms,                where the heterocycle has at most one sulfur atom;

In one aspect, a suitable thiazolium dye may have Formula IV below:

wherein R₈ and R₉ may be identical or different and, independently ofone another, may be a saturated or unsaturated (C₁-C₂₂)-alkyl group, a(C₁-C₂₂)-alkyl group, a hydroxy-(C₂-C₂₂)-alkyl group optionallyinterrupted by oxygen, a polyether group derived from ethylene oxide,propylene oxide or butylene oxide, an amino-(C₁-C₂₂)-alkyl group, asubstituted or unsubstituted phenyl group or a benzyl group, a(C₁-C₂₂)-alkyl group terminated in sulfonate, sulfate, or carboxylate,or R₈ and R₉, together with the nitrogen atom, may form a 5-membered to6-membered ring system, which may comprise a further heteroatom; or R₈or R₉ may form, with a carbon atom of the benzene ring, an optionallyoxygen-containing or nitrogen containing five or six-memberedheterocycle which may be substituted with one or more (C₁-C₂₂)-alkylgroups, and mixtures thereof, and R₁₀ is hydrogen or methyl. For FormulaIV, Q⁻ is as described for Formula I above.

In one aspect, suitable thiazolium dyes may have Formula (V);

wherein:

-   -   a.) R₁ may be selected from a branched or unbranched        (C₁-C₂₂)-alkyl moiety, an aromatic alkyl moiety, a polyalkylene        oxide moiety or a moiety having Formula (VI) below;

-   -   -   wherein            -   (i) R₂ may be selected from hydrogen, methyl, ethyl,                propyl, acetate or a hydroxyl moiety; m and p may be,                independently, integers from 0 to (n−1), with the                proviso that n is an integer from 1 to 6 and m+p=(n−1)            -   (ii) Y may be selected from a hydroxyl, sulfonate,                sulfate, carboxylate or acetate moiety;

    -   b.) R₃ and R₄:        -   i.) may be independently selected from hydrogen; a saturated            or unsaturated (C₁-C₂₂)-alkyl moiety; a            hydroxy-(C₂-C₂₂)-alkyl moiety; a hydroxy-(C₂-C₂₂)-alkyl            moiety comprising, in addition to the hydroxyl oxygen, an            oxygen atom; a polyether moiety; an amino-(C₁-C₂₂)-alkyl            moiety; a substituted or unsubstituted phenyl moiety; a            substituted or unsubstituted benzyl moiety; a (C₁-C₂₂)-alkyl            moiety terminated in sulfonate, sulfate, acetate, or            carboxylate; or        -   ii.) when taken together may form a saturated or unsaturated            heterocyclic or carbocyclic moiety; or        -   iii.) when taken together may form a saturated or            unsaturated heterocyclic or carbocyclic moiety substituted            by, sulfate, sulfonate, phosphate, nitrate, and carboxylate;

    -   c.) X may be moiety having Formula VII below;

-   -   -   wherein:        -   i.) R₅ and R₆:            -   (a) may be independently selected from hydrogen; a                saturated or unsaturated (C₁-C₂₂)-alkyl moiety; a                hydroxy-(C₂-C₂₂)-alkyl moiety; a hydroxy-(C₂-C₂₂)-alkyl                moiety comprising, in addition to the hydroxyl oxygen,                an oxygen atom; a capped or uncapped polyether moiety;                an amino-(C₁-C₂₂)-alkyl moiety; a substituted or                unsubstituted phenyl moiety; a substituted or                unsubstituted benzyl moiety; a (C₁-C₂₂)-alkyl moiety                comprising a terminating C₁-C₄ alkyl ether, sulfonate,                sulfate, acetate or carboxylate moiety; a thiazole                moiety or            -   (b) when taken together may form a saturated or                unsaturated heterocyclic moiety; or            -   (c) when taken together form a saturated or unsaturated                heterocyclic moiety substituted by one or more,                alkoxylate, sulfate, sulfonate, phosphate, nitrate,                and/or carboxylate moieties;            -   (d) when taken together with R₇, R₈, or R₇ and R₈ form                one or more saturated or unsaturated heterocyclic                moieties, optionally substituted by one or more                alkoxylate, sulfate, sulfonate, phosphate, nitrate,                and/or carboxylate moieties; or            -   (e) when taken together form a thiazole moiety;        -   ii.) R₇ and R₈ may be independently selected from hydrogen            or a saturated or unsaturated alkyl moiety;

    -   d.) Q⁻ may be an anion that balances the overall charge of the        compound of Formula I, and the index q is 0 or 1. Suitable        anions include chloro, bromo, methosulfate, tetrafluoroborate,        and acetate anions.

In one aspect, for Formula V:

a.) R₁ may be a methyl moiety;

b.) R₃ and R₄ may be hydrogen; and

c.) X may have Formula VIII below:

wherein

-   -   (i) R₅ and R₆ may be as defined for Formula VII above;    -   (ii) R₇ may be hydrogen or a methyl moiety; and    -   (iii) R₈ may be hydrogen.

In one aspect, for Formula VII R₅ and R₆ each comprise, independently,from 1 to 20 alkylene oxide units and, independently, a moiety selectedfrom the group consisting of: styrene oxide, glycidyl methyl ether,isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidylether, 2-ethylhexylgycidyl ether, or glycidylhexadecyl ether.

Suitable polymeric dyes include polymeric dyes selected from the groupconsisting of polymers containing conjugated chromogens (dye-polymerconjugates) and polymers with chromogens co-polymerised into thebackbone of the polymer and mixtures thereof.

In another aspect, suitable polymeric dyes include polymeric dyesselected from the group consisting of fabric-substantive colorants soldunder the name of Liquitint® (Milliken, Spartanburg, S.C., USA),dye-polymer conjugates formed from at least one reactive dye and apolymer selected from the group consisting of polymers comprising amoiety selected from the group consisting of a hydroxyl moiety, aprimary amine moiety, a secondary amine moiety, a thiol moiety andmixtures thereof. In still another aspect, suitable polymeric dyesinclude polymeric dyes selected from the group consisting of Liquitint®(Milliken, Spartanburg, S.C., USA) Violet CT, carboxymethyl cellulose(CMC) conjugated with a reactive blue, reactive violet or reactive reddye such as CMC conjugated with C.I. Reactive Blue 19, sold by Megazyme,Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product codeS-ACMC and mixtures thereof.

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay, and mixtures thereof. In another aspect, suitable dye clayconjugates include dye clay conjugates selected from the groupconsisting of one cationic/basic dye selected from the group consistingof C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I.Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through23, CI Basic Black 1 through 11, and a clay selected from the groupconsisting of Montmorillonite clay, Hectorite clay, Saponite clay andmixtures thereof. In still another aspect, suitable dye clay conjugatesinclude dye clay conjugates selected from the group consisting ofMontmorillonite Basic Blue B7 C.I. 42595 conjugate, MontmorilloniteBasic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I.42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate,Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I.Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate,Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite BasicBlue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite BasicRed R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate andmixtures thereof.

Suitable pigments include pigments selected from the group consisting offlavanthrone, indanthrone, chlorinated indanthrone containing from 1 to4 chlorine atoms, pyranthrone, dichloropyranthrone,monobromodichloropyranthrone, dibromodichloropyranthrone,tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide,wherein the imide groups may be unsubstituted or substituted byC₁-C₃-alkyl or a phenyl or heterocyclic radical, and wherein the phenyland heterocyclic radicals may additionally carry substituents which donot confer solubility in water, anthrapyrimidinecarboxylic acid amides,violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyaninewhich may contain up to 2 chlorine atoms per molecule, polychloro-copperphthalocyanine or polybromochloro-copper phthalocyanine containing up to14 bromine atoms per molecule and mixtures thereof. In another aspect,suitable pigments include pigments selected from the group consisting ofUltramarine Blue (C.I. Pigment Blue 29), Ultramarine Violet (C.I.Pigment Violet 15) and mixtures thereof.

The aforementioned fabric hueing agents can be used in combination (anymixture of fabric hueing agents can be used). Suitable fabric hueingagents can be purchased from Aldrich, Milwaukee, Wis., USA; CibaSpecialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany;Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., EastProvidence, R.I., USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen,Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland;Avecia, Manchester, UK and/or made in accordance with the examplescontained herein.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

Catalytic Metal Complexes—Applicants' compositions may include catalyticmetal complexes. One type of metal-containing bleach catalyst is acatalyst system comprising a transition metal cation of defined bleachcatalytic activity, such as copper, iron, titanium, ruthenium, tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methyl-enephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. Nos. 5,597,936 and 5,595,967. Such cobaltcatalysts are readily prepared by known procedures, such as taught forexample in U.S. Pat. Nos. 5,597,936, and 5,595,967.

Compositions herein may also suitably include a transition metal complexof a macropolycyclic rigid ligand—abbreviated as “MRL”. As a practicalmatter, and not by way of limitation, the compositions and cleaningprocesses herein can be adjusted to provide on the order of at least onepart per hundred million of the benefit agent MRL species in the aqueouswashing medium, and may provide from about 0.005 ppm to about 25 ppm,from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about5 ppm, of the MRL in the wash liquor.

Suitable transition-metals in the instant transition-metal bleachcatalyst include manganese, iron and chromium. Suitable MRL's herein area special type of ultra-rigid ligand that is cross-bridged such as5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexa-decane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

Rheology Modifier

The liquid compositions of the present invention may comprise a rheologymodifier. The rheology modifier may be selected from the groupconsisting of non-polymeric crystalline, hydroxy-functional materials,polymeric rheology modifiers which impart shear thinning characteristicsto the aqueous liquid matrix of the composition. In one aspect, suchrheology modifiers impart to the aqueous liquid composition a high shearviscosity, at 20 sec⁻¹ shear rate and at 21° C., of from 1 to 7000 cpsand a viscosity at low shear (0.5 sec⁻¹ shear rate at 21° C.) of greaterthan 1000 cps, or even 1000 cps to 200,000 cps. In one aspect, forcleaning and treatment compositions, such rheology modifiers impart tothe aqueous liquid composition a high shear viscosity, at 20 sec⁻¹ andat 21° C., of from 50 to 3000 cps and a viscosity at low shear (0.5sec⁻¹ shear rate at 21° C.) of greater than 1000 cps, or even 1000 cpsto 200,000 cps. Viscosity according to the present invention is measuredusing an AR 2000 rheometer from TA instruments using a plate steelspindle having a plate diameter of 40 mm and a gap size of 500 μm. Thehigh shear viscosity at 20 sec⁻¹ and low shear viscosity at 0.5 sec⁻¹can be obtained from a logarithmic shear rate sweep from 0.1 sec⁻¹ to 25sec⁻¹ in 3 minutes time at 21° C. Crystalline hydroxyl functionalmaterials are rheology modifiers which form thread-like structuringsystems throughout the matrix of the composition upon in situcrystallization in the matrix. Polymeric rheology modifiers arepreferably selected from polyacrylates, polymeric gums, other non-gumpolysaccharides, and combinations of these polymeric materials.

Generally the rheology modifier will comprise from 0.01% to 1% byweight, preferably from 0.05% to 0.75% by weight, more preferably from0.1% to 0.5% by weight, of the compositions herein.

Structuring agents which are especially useful in the compositions ofthe present invention may comprise non-polymeric (except forconventional alkoxylation), crystalline hydroxy-functional materialswhich can form thread-like structuring systems throughout the liquidmatrix when they are crystallized within the matrix in situ. Suchmaterials can be generally characterized as crystalline,hydroxyl-containing fatty acids, fatty esters or fatty waxes. In oneaspect, rheology modifiers include crystalline, hydroxyl-containingrheology modifiers include castor oil and its derivatives. In oneaspect, rheology modifiers include may be hydrogenated castor oilderivatives such as hydrogenated castor oil and hydrogenated castor wax.Commercially available, castor oil-based, crystalline,hydroxyl-containing rheology modifiers include THIXCIN™ from Rheox, Inc.(now Elementis).

Other types of rheology modifiers, besides the non-polymeric,crystalline, hydroxyl-containing rheology modifiers describedheretofore, may be utilized in the liquid detergent compositions herein.Polymeric materials which provide shear-thinning characteristics to theaqueous liquid matrix may also be employed.

Suitable polymeric rheology modifiers include those of the polyacrylate,polysaccharide or polysaccharide derivative type. Polysaccharidederivatives typically used as rheology modifiers comprise polymeric gummaterials. Such gums include pectine, alginate, arabinogalactan (gumArabic), carrageenan, gellan gum, xanthan gum and guar gum.

If polymeric rheology modifiers are employed herein, a preferredmaterial of this type is gellan gum. Gellan gum is aheteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC31461. Gellan gum is commercially marketed by CP Kelco U.S., Inc. underthe KELCOGEL tradename.

A further alternative and suitable rheology modifier include acombination of a solvent and a polycarboxylate polymer. Morespecifically the solvent may be an alkylene glycol. In one aspect, thesolvent may comprise dipropylene glycol. In one aspect, thepolycarboxylate polymer may comprise a polyacrylate, polymethacrylate ormixtures thereof. In one aspect, solvent may be present, based on totalcomposition weight, at a level of from 0.5% to 15%, or from 2% to 9% ofthe composition. In one aspect, polycarboxylate polymer may be present,based on total composition weight, at a level of from 0.1% to 10%, orfrom 2% to 5%. In one aspect, the may comprise mixture of dipropyleneglycol and 1,2-propanediol. In one solvent component aspect, the ratioof dipropylene glycol to 1,2-propanediol may be 3:1 to 1:3, or even 1:1.In one aspect, the polyacrylate may comprise a copolymer of unsaturatedmono- or di-carbonic acid and C₁-C₃₀ alkyl ester of the (meth) acrylicacid. In another aspect, the rheology modifier may comprise apolyacrylate of unsaturated mono- or di-carbonic acid and C₁-C₃₀ alkylester of the (meth) acrylic acid. Such copolymers are available fromNoveon Inc under the tradename Carbopol Aqua 30®.

In the absence of rheology modifier and in order to impart the desiredshear thinning characteristics to the liquid composition, the liquidcomposition can be internally structured through surfactant phasechemistry or gel phases.

Silicone Emulsion

The compositions of the present invention can comprise a siliconeemulsion. An emulsion is a mixture of one liquid (the dispersed phase)dispersed in another (the continuous phase). In the context of thepresent, silicone emulsion also encompasses macroemulsion andmicroemulsion.

In one embodiment, the silicone emulsion of the present invention isadded as an emulsion of Silicone oil in water or a solvent containingwatery solution in a range of 35-65 (w/w %). In one embodiment, thesilicone emulsion of the present invention can be any silicone emulsion.

In one embodiment the mean particle size of the Silicone emulsion is0.01 to 2 micrometer, more preferable from 0.2 to 0.8 micrometer meanparticle size.

Preferably, the emulsified silicone oil is selected from the groupcomprising non-ionic nitrogen free silicone oils, aminofunctionalsilicone oils and mixtures thereof.

In one embodiment of the present invention, the silicone emulsion is anaminofunctional silicone, preferably aminodimethicone.

In a preferred embodiment of the present invention, the siliconeemulsion is a non-ionic nitrogen free silicone emulsion, preferably,selected from the group comprising polydialkyl silicone, polydimethylsilicone, alkyloxylated silicone, ethoxylated silicone, propoxylatedsilicone, ethoxylated propoxylated silicone, quaternary silicone orderivatives thereof and mixtures thereof. In a more preferredembodiment, the non-ionic nitrogen free silicone emulsion is selectedfrom the group comprising polydialkyl silicone, polydimethyl siliconeand mixtures thereof. In one embodiment, the silicone emulsion ispolydimethyl silicone.

In this preferred embodiment, wherein the silicone emulsion ispolydimethyl silicone, the polydimethyl silicone has a viscosity between0.0001 m²·s⁻¹ and 0.1 m²·s⁻¹, preferably between 0.0003 m²·s⁻¹ and 0.06m²·s⁻¹, more preferably between 0.00035 m²·s⁻¹ and 0.012 m²·s⁻¹.

Suitable solvents for use in the solvent containing watery solution canbe selected from the group comprising C1-C20 linear, branched, cyclic,saturated and/or unsaturated alcohols with one or more free hydroxygroups; amines, alkanolamines, and mixtures thereof. Preferred solventsare monoalcohols, diols, monoamine derivatives, glycerols, glycols, andmixtures thereof, such as ethanol, propanol, propandiol,monoethanolamin, glycerol, sorbitol, alkylene glycols, polyalkyleneglycols, and mixtures thereof. Most preferred solvents are selected fromthe group comprising 1,2-propandiol, 1.3-propandiol, glycerol, ethyleneglycol, diethyleneglycol, and mixtures thereof.

The emulsion contains a water soluble emulsifier, selected from thegroup of commercially available emulsifiers encompassing cationic,anionic, nonionic or zwitter—ionic emulsifiers. In a preferredembodiment of this invention the emulsifier is a nonionic surfactant.

Alternatively premixes of silicone emulsions and solvents are utilizedin order to overcome process problems in terms of proper dispersion ordissolution of all ingredients throughout the composition.

Premixes of the silicone emulsion in the context of the presentinvention, include high internal phase emulsion (“HIPE”). That isachieved by premixing a silicone emulsion, such as polydimethylsilicone, and an emulsifier to create a HIPE, then mixing this HIPE intothe composition, thereby achieving good mixing resulting in anhomogeneous mixture. Such HIPEs are comprised of at least 65%,alternatively at least 70%, alternatively at least 74%, alternatively atleast 80%; alternatively not greater than 95%, by weight of an internalphase (dispersed phase), wherein the internal phase may comprise asilicone emulsion. The internal phase can also be other water insolublefabric care benefit agents that are not already pre-emulsified. Theinternal phase is dispersed by using an emulsifying agent. Examples ofthe emulsifying agent include a surfactant or a surface tension reducingpolymer. In one embodiment, the range of the emulsifying agent is fromat least 0.1% to 25%, alternatively from 1% to 10%, and alternativelyfrom 2% to 6% by weight of the HIPE. In another embodiment, theemulsifying agent is water soluble and reduces the surface tension ofwater, at a concentration less than 0.1% by weight of deionized water,to less than 0.0007 N (70 dynes), alternatively less than 0.0006 N (60dynes), alternatively less than 0.0005 N (50 dynes); alternatively at orgreater than 0.0002 N (20 dynes). In another embodiment, the emulsifyingagent is at least partially water insoluble.

The external phase (continuous phase), in one embodiment, is water,alternatively may comprise at least some water, alternatively maycomprise little or no water. In another embodiment, the external phaseof water may comprise from less than 35%, alternatively less than 30%,alternatively less than 25%; alternatively at least 1%, by weight ofHIPE. Non-aqueous HIPEs can be prepared as well with a solvent as theexternal phase with low or no water present. Typical solvents includeglycerin and propylene glycol.

In another embodiment, the composition is a non-concentratedcomposition. In this embodiment, the silicone emulsion is not, at leastinitially, emulsified and can be emulsified in the fabric carecomposition itself.

The composition of the present invention may comprise a siliconeemulsion which acts to maintain the physical stability of the liquidfabric softening composition following a freeze-thaw cycle and also uponprolonged storage at low temperatures.

The silicone emulsion of the present invention is at a level from 0.5%to 10%. In another embodiment, the silicone emulsion of the presentinvention is at a level from 0.3% to 10%, preferably from 0.3% to 5%,and most preferably from 0.5% to 3.0% by weight of the liquid fabricsoftening composition.

I. Non-Ionic Nitrogen Free Silicone Emulsions:

In the context of the present invention, preferably the siliconeemulsion is selected from the group comprising non-ionic nitrogen freesilicone emulsions having the formulae (I), (II), (III), and mixturesthereof:

wherein each R¹ is independently selected from the group consisting oflinear, branched or cyclic substituted or unsubstituted alkyl groupshaving from 1 to 20 carbon atoms; linear, branched or cyclic substitutedor unsubstituted alkenyl groups having from 2 to 20 carbon atoms;substituted or unsubstituted aryl groups having from 6 to 20 carbonatoms; substituted or unsubstituted alkylaryl, substituted orunsubstituted arylalkyl and substituted or unsubstituted arylalkenylgroups having from 7 to 20 carbon atoms and mixtures thereof; each R² isindependently selected from the group consisting of linear, branched orcyclic substituted or unsubstituted alkyl groups having from 1 to 20carbon atoms; linear, branched or cyclic substituted or unsubstitutedalkenyl groups having from 2 to 20 carbon atoms; substituted orunsubstituted aryl groups having from 6 to 20 carbon atoms; substitutedor unsubstituted alkylaryl groups, substituted or unsubstitutedarylalkyl, substituted or unsubstituted arylalkenyl groups having from 7to 20 carbon atoms and from a poly(ethyleneoxide/propyleneoxide)copolymer group having the general formula;

—(CH₂)_(n)O(C₂H₄O)_(c)(C₃H₆O)_(d)R³  (IV)

polydialkyl silicone, polydimethyl silicone, alkyloxylated silicone,quaternary silicone with at least one R² being apoly(ethyleneoxy/propyleneoxy) copolymer group (ethoxylated silicone,propoxylated silicone, ethoxylated propoxylated silicone emulsions), andeach R³ is independently selected from the group consisting of hydrogen,an alkyl having 1 to 4 carbon atoms, an acetyl group, and mixturesthereof, wherein the index w has the value as such that the viscosity ofthe nitrogen-free silicone polymer of formulae (I) and (III) is between0.0001 m²·s⁻¹ (100 centistokes) and 0.1 m²·s⁻¹ (100,000 centistokes);wherein a is from 1 to 50; b is from 1 to 50; n is 1 to 50; total c (forall polyalkyleneoxy side groups) has a value of from 1 to 100; total dis from 0 to 14; total c+d has a value of from 5 to 150

More preferably, the non-ionic nitrogen free silicone emulsion isselected from the group consisting of linear non-ionic nitrogen-freesilicone emulsions having the formulae (II) to (III) as above, whereinR¹ is selected from the group consisting of methyl, phenyl, phenylalkyl,and mixtures thereof; wherein R² is selected from the group consistingof methyl, phenyl, phenylalkyl, and mixtures thereof; and from the grouphaving the general formula (IV), as defined above, and mixtures thereof;wherein R³ is defined as above and wherein the index w has a value suchthat the viscosity of the nitrogen-free silicone emulsion of formula(III) is between 0.0001 m²·s⁻¹ (100 centistokes) and 0.1 m²·s⁻¹ (100,000centistokes); a is from 1 to 30, b is from 1 to 30, n is from 3 to 5,total c is from 6 to 100, total d is from 0 to 3, and total c+d is from7 to 100.

Most preferably, the nitrogen-free silicone emulsion is selected fromthe group comprising linear non-ionic nitrogen free silicone emulsionshaving the general formula (III) as above, wherein R¹ is methyl, i.e.the silicone emulsion is polydimethyl silicone In this preferredembodiment, wherein the silicone emulsion is polydimethyl silicone,index w has a value such that the polydimethyl silicone has a viscositybetween 0.0001 m²·s⁻¹ and 0.1 m²·s⁻¹, preferably between 0.0003 m²·s⁻¹and 0.06 m²·s⁻¹, more preferably between 0.00035 m²·s⁻¹ and 0.012m²·s⁻¹.

II. Aminofunctional Silicone Emulsions:

In one embodiment of the present invention, the silicone emulsion is anaminofunctional silicone. Aminofunctional silicone emulsions arematerials of the formula:

HO[Si(CH₃)₂—O]_(x){Si(OH)[(CH₂)₃—NH—(CH₂)₂—NH₂]O}_(y)H

wherein x and y are integers which depend on the viscosity of thesilicone emulsion. Preferably, the aminofunctional silicone emulsion hasa molecular weight such that it exhibits a viscosity of from 0.0005m²·s⁻¹ (500 centistokes) to 0.5 m²·s⁻¹ (500,000 centistokes). Thismaterial is also known as “aminodimethicone.

Method of Use

Certain of the consumer products disclosed herein can be used to cleanor treat a situs inter alia a surface or fabric. Typically at least aportion of the situs is contacted with an embodiment of Applicants'composition, in neat form or diluted in a liquor, for example, a washliquor and then the situs may be optionally washed and/or rinsed. In oneaspect, a situs is optionally washed and/or rinsed, contacted with aparticle according to the present invention or composition comprisingsaid particle and then optionally washed and/or rinsed. In one aspect, amethod of cleaning or treating a situs comprising optionally washingand/or rinsing said situs, contacting said situs with the compositionselected from the compositions and mixtures thereof disclosed herein andoptionally washing and/or rinsing said situs is disclosed. For purposesof the present invention, washing includes but is not limited to,scrubbing, and mechanical agitation. The fabric may comprise most anytype of fiber capable of being laundered or treated in normal consumeruse conditions. Liquors that may comprise the disclosed compositions mayhave a pH of from about 3 to about 11.5. Such compositions are typicallyemployed at concentrations of from about 500 ppm to about 15,000 ppm insolution. When the wash solvent is water, the water temperaturetypically ranges from about 5° C. to about 90° C. and, when the situscomprises a fabric, the water to fabric ratio is typically from about1:1 to about 30:1.

TEST METHODS

-   -   1.) Average Molecular Mass: For purposes of the present        specification and claims, the average molecular mass of a        polymer is determined in accordance with ASTM Method ASTM        D4001-93 (2006).    -   2.) Hydrolysis Degree: For purposes of the present specification        and claims, hydrolysis degree is determined in accordance with        the method found in U.S. Pat. No. 6,132,558, column 2, line 36        to column 5, line 25.    -   3.) Charge Density: For purposes of the present specification        and claims, the charge density of a polymer is determined with        the aid of colloid titration, cf. D. Horn, Progress in Colloid &        Polymer Sci. 65 (1978), 251-264.    -   4.) Zeta Potential: For purposes of the present specification        and claims, zeta potential is determined as follows:        -   a.) Equipment: Malvern Zetasizer 3000        -   b.) Procedure for sample preparation:            -   (i) Add 5 drops of slurry containing the encapsulate of                interest to 20 mL 1 mM NaCl solution to dilute the                slurry. The concentration may need adjustment to make                the count rate in the range of 50 to 300 Kcps.            -   (ii) the zeta potential is measured on the diluted                sample without filtration            -   (iii) inject the filtered slurry in the Zetasizer cell                and insert the cell in the equipment. Test temperature                is set at 25° C.            -   (iv) when the temperature is stable (usually in 3 to 5                minutes), measurement is started. For each sample, five                measuresments are taken. Three samples are taken for                each slurry of interest. The average of the 15 readings                is calculated.        -   c.) Equipment settings for the measurements:            -   Parameters settings for the sample used:            -   Material: melamine R11,680, absorption 0.10            -   Dispersant: NaCL 1 mM            -   Temperature: 25° C.            -   Viscosity: 0.8900 cP            -   RI: 1.330            -   Dielecectric constant: 100            -   F(ka) selection: Model: Smoluchowski F(ka) 1.5            -   Use dispersant viscosity as sample viscosity            -   Cell type: DTS 1060C: clear disposable Zeta cells            -   Measurements: 3 measurements        -   d.) Results: Zeta potential is reported in mV as the average            of the 15 readings taken for the slurry of interest.

EXAMPLES

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

Example 1 84 Wt % Core/16 Wt % Wall Melamine Formaldehyde (MF) Capsule

25 grams of butyl acrylate-acrylic acid copolymer emulsifier (ColloidC351, 25% solids, pka 4.5-4.7, (Kemira Chemicals, Inc. Kennesaw, Ga.U.S.A.) is dissolved and mixed in 200 grams deionized water. The pH ofthe solution is adjusted to pH of 4.0 with sodium hydroxide solution. 8grams of partially methylated methylol melamine resin (Cymel 385, 80%solids, (Cytec Industries West Paterson, N.J., U.S.A.)) is added to theemulsifier solution. 200 grams of perfume oil is added to the previousmixture under mechanical agitation and the temperature is raised to 50°C. After mixing at higher speed until a stable emulsion is obtained, thesecond solution and 4 grams of sodium sulfate salt are added to theemulsion. This second solution contains 10 grams of butylacrylate-acrylic acid copolymer emulsifier (Colloid C351, 25% solids,pka 4.5-4.7, Kemira), 120 grams of distilled water, sodium hydroxidesolution to adjust pH to 4.8, 25 grams of partially methylated methylolmelamine resin (Cymel 385, 80% solids, Cytec). This mixture is heated to70° C. and maintained overnight with continuous stifling to complete theencapsulation process. 23 grams of acetoacetamide (Sigma-Aldrich, SaintLouis, Mo., U.S.A.) is added to the suspension. An average capsule sizeof 30 um is obtained as analyzed by a Model 780 Accusizer.

Example 2 Procedure for Preparing Polymer Coated Perfume Microcapsules

Polymer coated perfume microcapsules are prepared by weighing 99 g ofmelamine formaldehyde perfume microcapsules reference slurry (99.75%)and the 1 g of Lupamin9030, 16% active (ex BASF, Ludwigshafen, Germany)in a glass jar. The two ingredients are shortly mixed with a spoon. Theyare further mixed overnight in a shaker.

Example 3 Procedure for Including Coated Perfume Microcapsules in aLiquid Laundry Detergent

74.9 g of compact liquid detergent free of perfume microcapsules isweighed and the 1.33 g of polymer coated perfume microcapsules is added.

The resulting product is mixed with a mechanical mixer for 1 minute.

Example 4

A 9 kg aliquot of perfume microcapsule slurry of Examples 2 is mixedusing a Eurostar mixer (IKA) with a R1382 attachment at a constant speedof 200 RPM. To the aliquot 500 g of carboxymethyl cellulose (CP Kelco)is added while mixing using the Eurostar mixer with same attachment andspeed as described above. The slurry is mixed for a total of two hoursor until a uniform paste is formed.

Example 5

1.28 kg of precipitated silica Sipernat® 22S (Degussa) is added to aF-20 paddle mixer (Forberg). The mixer is run initially for 5 seconds todistribute the silica evenly on the base of the mixer. The mixer isstopped and 8.25 kg of paste, made according to Example 4, is evenlydistributed onto the powder. The mixer is then run at 120 rpm for atotal of 30 seconds. Following mixing, the wet particles are dumped outof the mixer and screened using a 2000 micron sieve to remove theoversize. The product passing through the screen is dried in 500 gbatches in a CDT 0.02 fluid bed dryer (Niro) to a final moisture contentof 20 wt % measured by Karl Fischer. The dryer is operated at an inlettemperature of 140° C. and air velocity of 0.68 m/s.

Examples 6-13

Examples of granular laundry detergent compositions comprising theperfume composition are included below.

% w/w of laundry detergent compositions Raw material 6 7 8 9 10 11 12 13Linear alkyl benzene 7.1 6.7 11.0 10.6 6.9 4.5 10.1 8.9 sulphonateSodium C₁₂₋₁₅ alkyl ethoxy 3.5 0.0 1.5 0.0 0.0 0.0 0.0 1.9 sulphatehaving a molar average degree of ethoxylation of 3 Acrylic Acid/MaleicAcid 3.6 1.8 4.9 2.0 1.0 1.6 3.9 2.3 Copolymer Sodium Alumino Silicate4.0 0.5 0.8 1.4 16.3 0.0 17.9 2.4 (Zeolite 4A) Sodium Tripolyphosphate0.0 17.5 0.0 15.8 0.0 23.3 0.0 0.0 Sodium Carbonate 23.2 16.8 30.2 17.318.4 9.0 20.8 30.0 Sodium Sulphate 31.4 29.4 35.5 7.2 26.3 42.8 33.228.3 Sodium Silicate 0.0 4.4 0.0 4.5 0.0 6.1 0.0 4.6 C₁₄₋₁₅ alkylethoxylated 0.4 2.6 0.8 2.5 3.1 0.3 3.8 0.4 alcohol having a molaraverage degree of ethoxylation of 7 Sodium Percarbonate 16.0 0.0 8.420.4 13.1 3.6 0.0 7.0 Sodium Perborate 0.0 9.9 0.0 0.0 0.0 0.0 0.0 0.0Tetraacetylethylenediamine 2.2 1.7 0.0 4.7 3.6 0.0 0.0 0.8 (TAED)Calcium Bentonite 0.0 0.0 0.0 1.8 0.0 0.0 0.0 5.6 Citric acid 2.0 1.52.0 2.0 2.5 1.0 2.5 1.0 Protease (84 mg active/g) 0.14 0.12 0.0 0.120.09 0.08 0.10 0.08 Amylase (22 mg active/g) 0.10 0.11 0.0 0.10 0.10 0.00.14 0.08 Lipase (11 mg active/g) 0.70 0.50 0.0 0.70 0.50 0.0 0.0 0.0Cellulase (2.3 mg active/g) 0.0 0.0 0.0 0.0 0.0 0.0 0.18 0.0 Benefitagent composition 1.4 0.6 0.8 1.0 0.7 0.3 0.7 1.2 of Example 5 Water &Miscellaneous Balance to 100%

The equipment and materials described in Examples 1 through to 19 can beobtained from the following: IKA Werke GmbH & Co. KG, Staufen, Germany;CP Kelco, Atlanta, United States; Forberg International AS, Larvik,Norway; Degussa GmbH, Diisseldorf, Germany; Niro A/S, Soeberg, Denmark;Baker Perkins Ltd, Peterborough, United Kingdom; Nippon Shokubai, Tokyo,Japan; BASF, Ludwigshafen, Germany; Braun, Kronberg, Germany; IndustrialChemicals Limited, Thurrock, United Kingdom; Primex ehf, Siglufjordur,Iceland; ISP World Headquarters; Polysciences, Inc. of Warrington, Pa.,United States; Cytec Industries Inc., New Jersey, United States;International Specialty Products, Wayne, N.J., United States; P&GChemicals Americas, Cincinnati, Ohio, United States; Sigma-AldrichCorp., St. Louis, Mo., United States, Dow Chemical Company of Midland,Mich., USA

Examples 14-23 Fabric Conditioner

Non-limiting examples of fabric conditioners containing the polymercoated perfume microcapsules disclosed in the present specification aresummarized in the following table.

EXAMPLES (% wt) 14 15 16 17 18 19 20 21 22 23 FSA ^(a) 14 16.47 14 12 1216.47 — — 5 10 FSA ^(b) — 3.00 — — — FSA ^(c) — — 6.5 — — Ethanol 2.182.57 2.18 1.95 1.95 2.57 — — 0.81 Isopropyl — — — — — — 0.33  1.22 —1.0— Alcohol Starch ^(d) 1.25 1.47 2.00 1.25 — 2.30 0.5  0.70 0.71 0.42Phase 0.21 0.25 0.21 0.21 0.14 0.18 0.15  0.14 0.2 0.1 StabilizingPolymer ^(f) Suds — — — — — — — 0.1 — — Suppressor ^(g) Calcium 0.150.176 0.15 0.15 0.30 0.176 — 0.1-0.15 — 0025. Chloride DTPA ^(h) 0.0170.017 0.017 0.017 0.007 0.007 0.20 — 0.002 0.002 Preservative 5 5 5 5 55 — 250 ^(j)   5 5 (ppm) ^(i, j) Antifoam^(k) 0.015 0.018 0.015 0.0150.015 0.015 — — 0.015 0.015 Silicone^(l) 1 — — 3 — — — — 1 — Dye (ppm)40 40 40 40 40 40 11 30-300 30 30 Ammonium 0.100 0.118 0.100 0.100 0.1150.115 — — — — Chloride HCl 0.012 0.014 0.012 0.012 0.028 0.028 0.016 0.025 0.011 0.011 Polymer 0.2 0.02 0.1 0.15 0.12 0.13 0.3 0.4 0.24 0.1coated perfume microcapsules as disclosed in Example 2 Additional 0.80.7 0.9 0.5 1.2 0.5 1.1 0.6 1.0 0.9 Neat Perfume Deionized † † † † † † †† † † Water ^(a) N,N-di(tallowoyloxyethyl)-N,N-dimethylammoniumchloride. ^(b) Methyl bis(tallow amidoethyl)2-hydroxyethyl ammoniummethyl sulfate. ^(c) Reaction product of Fatty acid withMethyldiethanolamine in a molar ratio 1.5:1, quaternized withMethylchloride, resulting in a 1:1 molar mixture ofN,N-bis(stearoyl-oxy-ethyl) N,N-dimethyl ammonium chloride andN-(stearoyl-oxy-ethyl) N,-hydroxyethyl N,N dimethyl ammonium chloride.^(d) Cationic high amylose maize starch available from National Starchunder the trade name CATO ®. ^(f) Rheovis CDE ex BASF. ^(g) SE39 fromWacker ^(h) Diethylenetriaminepentaacetic acid. ^(i) KATHON ® CGavailable from Rohm and Haas Co. “PPM” is “parts per million.” ^(j)Gluteraldehyde ^(k)Silicone antifoam agent available from Dow CorningCorp. under the trade name DC2310. ^(l)Silicone emulsion, availableunder the trade name E3500 supplied by Wacker † balance

Examples 24-29 Liquid Laundry Formulations (HDLs)

Ingredient 24 25 26 27 28 29 Alkyl Ether Sulphate 0.00 0.50 12.0 12.06.0 7.0 Dodecyl Benzene 8.0 8.0 1.0 1.0 2.0 3.0 Sulphonic AcidEthoxylated Alcohol 8.0 6.0 5.0 7.0 5.0 3.0 Citric Acid 5.0 3.0 3.0 5.02.0 3.0 Fatty Acid 3.0 5.0 5.0 3.0 6.0 5.0 Ethoxysulfated 1.9 1.2 1.52.0 1.0 1.0 hexamethylene diamine quaternized Diethylene triamine penta0.3 0.2 0.2 0.3 0.1 0.2 methylene phosphonic acid Enzymes 1.20 0.80 01.2 0 0.8 Brightener (disulphonated 0.14 0.09 0 0.14 0.01 0.09 diaminostilbene based FWA) Cationic hydroxyethyl 0 0 0.10 0 0.200 0.30cellulose Poly(acrylamide-co- 0 0 0 0.50 0.10 0 diallyldimethylammoniumchloride) Hydrogenated Castor Oil 0.50 0.44 0.2 0.2 0.3 0.3 StructurantBoric acid 2.4 1.5 1.0 2.4 1.0 1.5 Ethanol 0.50 1.0 2.0 2.0 1.0 1.0 1,2propanediol 2.0 3.0 1.0 1.0 0.01 0.01 Glutaraldehyde 0 0 19 ppm 0 13 ppm0 Diethyleneglycol (DEG) 1.6 0 0 0 0 0 2,3-Methyl-1,3- 1.0 1.0 0 0 0 0propanediol (M pdiol) Mono Ethanol Amine 1.0 0.5 0 0 0 0 NaOH SufficientTo pH 8 pH 8 pH 8 pH 8 pH 8 pH 8 Provide Formulation pH of: SodiumCumene 2.00 0 0 0 0 0 Sulphonate (NaCS) Silicone (PDMS) emulsion 0.0030.003 0.003 0.003 0.003 0.003 Neat Perfume 0.02 0.15 0.0 0.2 0.3 0.1Polymer coated perfume 0.2 0.02 0.1 0.15 0.12 0.13 microcapsules asdisclosed in Example 2 Water Balance Balance Balance Balance BalanceBalance

Example 30 Shampoo Formulation

Ingredient Ammonium Laureth Sulfate (AE₃S) 6.00 Ammonium Lauryl Sulfate(ALS) 10.00 Laureth-4 Alcohol 0.90 Trihydroxystearin⁽⁷⁾ 0.10 Polymercoated perfume 0.60 microcapsules as disclosed in Example 2 SodiumChloride 0.40 Citric Acid 0.04 Sodium Citrate 0.40 Sodium Benzoate 0.25Ethylene Diamine Tetra Acetic Acid 0.10 Dimethicone^((9,10,11)) 1.00⁽⁹⁾Water and Minors (QS to 100%) Balance

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. An encapsulate comprising a core, a wall havingan outer surface and a coating, said wall encapsulating said core, saidcoating coating the outer surface of said wall, said coating comprisingone or more efficiency polymers having the following formula:

wherein: a) wherein a and b are integers or averages (real numbers) fromabout 50-100,000; b) each R₁ is independently selected from H, CH₃,(C═O)H, alkylene, alkylene with unsaturated C—C bonds, CH₂—CROH,(C═O)—NH—R, (C═O)—(CH₂)_(n)—OH, (C═O)—R, (CH₂)_(n)-E,—(CH₂—CH(C═O))_(n)—XR, —(CH₂)_(n)—COOH, —(CH₂)_(n)—NH₂,—(CH₂)_(n)—(C═O)NH₂, the index n is a integer from about 0 to about 24,E is an electrophilic group; R is a saturated or unsaturated alkane,dialkylsiloxy, dialkyloxy, aryl, alkylated aryl, that may furthercontain a moiety selected from the group consisting of cyano, OH, COOH,NH₂, NHR, sulfonate, sulphate, —NH₂, quaternized amines, thiols,aldehyde, alkoxy, pyrrolidone, pyridine, imidazol, imidazolinium halide,guanidine, phosphate, monosaccharide, oligo or polysaccharide; c) R₂ orR₃ can be absent or present: (i) when R₃ is present each R₂ isindependently selected from the group consisting of —NH₂, —COO—,—(C═O)—, —O—, —S—, —NH—(C═O)—, —NR₁—, dialkylsiloxy, dialkyloxy,phenylene, naphthalene, alkyleneoxy; and each R₃ is independentlyselected the same group as R₁; (ii) when R₃ is absent each R₂ isindependently selected from the group consisting of —NH₂, —COO—,—(C═O)—, —O—, —S—, —NH—(C═O)—, —NR₁—, dialkylsiloxy, dialkyloxy,phenylene, naphthalene, alkyleneoxy; and each R₃ is independentlyselected the same group as R₁; and (iii) when R₂ is absent, each R₃ isindependently selected the same group as R₁; d) said one or moreefficiency polymers having an average molecular mass from about 1,000 Dato about 50,000,000 Da; a hydrolysis degree, when said efficiencypolymer is a polyvinyl formamide, of from about 5% to about 95%, and/ora charge density from about 1 meq/g efficiency polymer to about 23 meq/gefficiency polymer.
 2. An encapsulate according to claim 1, wherein saidone or more efficiency polymers is selected from the group consisting ofpolyvinyl amines, polyvinyl formamides, and polyallyl amines andcopolymers thereof.
 3. An encapsulate according to claim 1, wherein saidcoating comprises one or more polyvinyl formamides.
 4. An encapsulateaccording to claim 1, having a coating to wall ratio of from about 1:200to about 1:2.
 5. An encapsulate according to claim 1, wherein; a) saidcore comprises a material selected from the group consisting ofperfumes; brighteners; dyes; insect repellants; silicones; waxes;flavors; vitamins; fabric softening agents; skin care agents in oneaspect, paraffins; enzymes; anti-bacterial agents; bleaches; sensates;and mixtures thereof; b) said wall comprises a material selected fromthe group consisting of polyethylenes; polyamides; polystyrenes;polyisoprenes; polycarbonates; polyesters; polyacrylates; aminoplasts,in one aspect said aminoplast comprises a polyureas, polyurethane,and/or polyureaurethane, in one aspect said polyurea comprisespolyoxymethyleneurea and/or melamine formaldehyde; polyolefins;polysaccharides, in one aspect alginate and/or chitosan; gelatin;shellac; epoxy resins; vinyl polymers; water insoluble inorganics;silicone; and mixtures thereof.
 6. An encapsulate according to claim 5,wherein said core comprises perfume and said wall comprises melamineformaldehyde and/or cross linked melamine formaldehyde.
 7. Anencapsulate according to claim 6, wherein said core comprises perfumeand said wall comprises melamine formaldehyde and/or cross linkedmelamine formaldehyde, poly(acrylic acid) and poly(acrylic acid-co-butylacrylate).
 8. A slurry comprising an encapsulate according to claim 1,said slurry having a zeta potential of from about −10 meV to about +50meV.
 9. A slurry comprising, based on total slurry weight, a sufficientamount of the encapsulate of claim 1 to provide said slurry with fromabout 0.05% to about 10% of the efficiency polymer.
 10. An agglomeratecomprising an encapsulate according to claim
 1. 11. A process of makingthe agglomerate of claim 10, said process comprising: a) combining anencapsulate according to claim 1; a plasticizer, and, optionally, abinder and/or chelant to form a mixture; b) combining said mixture withsaid dusting agent; and c) removing a sufficient amount of saidplasticizer from said material to yield a product comprising, based ontotal product weight from 1% to 50% plasticizer.
 12. A consumer productcomprising: a) an encapsulate according to claim 1; and b) an adjunctingredient.
 13. The consumer product of claim 12, said consumer productcomprising a sufficient amount of encapsulate to provide said consumerproduct with an efficiency polymer level, based on total consumerproduct weight, of from about 0.0001% to about 0.1%.
 14. A consumerproduct according to claim 12, said consumer product comprising amaterial selected from the group consisting of an anionic surfactant,cationic surfactant, silicone and mixtures thereof, said consumerproduct having: a) an anionic surfactant to efficiency polymer ratio offrom about 100.000:1 to about 1:1; b) a cationic surfactant toefficiency polymer ratio of from about 100.000:1 to about 1:1; and/or c)a silicone to efficiency polymer ratio of from about 100.000:1 to about1:1.
 15. A consumer product according to claim 12 wherein said adjunctingredient is selected from the group consisting of polymers, in oneaspect, a cationic polymer, surfactants, builders, chelating agents,optical brighteners, dye transfer inhibiting agents, dispersants,enzymes, enzyme stabilizers, catalytic materials, bleach activators,polymeric dispersing agents, clay soil removal/anti-redeposition agents,brighteners, dye polymer conjugates; dye clay conjugates, sudssuppressors, dyes, bleach catalysts, additional perfume and/or perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids, rheology modifiers,structurants, thickeners, pigments, water and mixtures thereof.
 16. Aconsumer product according to claim 15, said consumer product comprisinga rheology modifier, thickener and/or structurant having a high shearviscosity, at 20 sec-1 shear rate and at 21° C., of from 1 to 7000 cpsand a viscosity at low shear (0.5 sec-1 shear rate at 21° C.) of greaterthan 1000 cps, or even 1000 cps to 200,000 cps.
 17. A consumer productaccording to claim 11, said consumer product being a fluid detergent andcomprising, based on total fluid detergent weight, less then about 80%water.
 18. A method of cleaning or treating a situs comprisingoptionally washing and/or rinsing said situs, contacting said situs witha composition according to claim 12, and optionally washing and/orrinsing said situs.
 19. A process of making a coated encapsulatecomprising combining an encapsulate according to claim 1 and a one ormore efficiency polymers.
 20. A process of making a coated encapsulateaccording to claim 19 wherein said encapsulate, when combined with saidone or more efficiency polymers, is contained in a slurry.
 21. A processof making a coated encapsulate according to claim 20 wherein asufficient amount of efficiency polymer is combined with said slurry toprovide said slurry with, based on total slurry weight, from about 0.05%to about 10% of said efficiency polymer.